Amine reaction compounds comprising one or more active ingredient

ABSTRACT

The present invention relates to a product of reaction between a primary and/or secondary amine and one or more active ingredients. By the present invention, there is provided a release of the active component over a longer period of time than by the use of the active itself.

FIELD OF THE INVENTION

The present invention relates to product of reaction between an amineand an active component, in particular an active aldehyde or ketone,more preferably an aldehyde or ketone perfume. More particularly, itrelates to such product of reaction for use in softening compositions.

BACKGROUND OF THE INVENTION

Perfumed products are well-known in the art. However, consumeracceptance of such perfumed products like softening products isdetermined not only by the performance achieved with these products butalso by the aesthetics associated therewith. The perfume components aretherefore an important aspect of the successful formulation of suchcommercial products.

It is also desired by consumers for treated fabrics to maintain thepleasing fragrance over time. Indeed, perfume additives make suchcompositions more aesthetically pleasing to the consumer, and in somecases the perfume imparts a pleasant fragrance to fabrics treatedtherewith. However, the amount of perfume carried-over from an aqueouslaundry bath onto fabrics is often marginal and does not last long onthe fabric. Furthermore, fragrance materials are often very costly andtheir inefficient use in laundry and cleaning compositions andineffective delivery to fabrics results in a very high cost to bothconsumers and laundry and cleaning manufacturers. Industry, therefore,continues to seek with urgency for more efficient and effectivefragrance delivery in laundry and cleaning products, especially forimprovement in the provision of long-lasting fragrance to the fabrics.

One solution is to use carrier mechanisms for perfume delivery, such asby encapsulation. This is taught in the prior art and described in U.S.Pat. No. 5,188,753.

Still another solution is to formulate compounds which provide a delayedrelease of the perfume over a longer period of time than by the use ofthe perfume itself. Disclosure of such compounds may be found in WO95/04809, WO 95/08976 and co-pending application EP 95303762.9.

However, notwithstanding the advances in the art, there is still a needfor a compound which provides a delayed release of the active component,in particular a perfume ingredient.

That need is even more acute for perfume ingredients which arecharacteristic of the fresh notes, namely the aldehydes and ketonesperfume ingredients. Indeed, whilst these provide a fresh fragrance,these perfumes are also very volatile and have a low substantivity onthe surface to be treated like fabrics.

Accordingly, it is a further object of the invention to provide asoftening composition comprising a perfume component which provides afresh fragrance and is substantive to the treated surface.

The Applicant has now found that specific reaction products of aminecompounds with an active aldehyde or ketone, such as imines compounds,also provide a delayed release of the active such as a perfume.

Imine compounds are known in the art under the name of Schiff baseswhich is the condensation of an aldehyde perfume ingredient with ananthranilate. A typical description can be found in U.S. Pat. No.4,853,369. By means of this compound, the aldehyde perfume is madesubstantive to the fabrics. However, a problem encountered with theseSchiff bases is that the methylanthranilate compound also exhibits astrong scent, which as a result produces a mixture of fragrances,thereby reducing or even inhibiting the aldehyde and/or ketone fragranceperception.

To achieve such perfume composition with comparable aldehyde or ketonesfresh notes whilst still having satisfactory fabric substantivity,perfumers have formulated around the composition. For example, by havinga carrier or encapsulating material for such notes such as withcyclodextrin, zeolites or starch.

Still another solution is the use of a glucosamine as described in JP09040687. However, this compound has been found to give a very lowstability in the wash process. As a result, insufficient perfumeresiduality on the treated fabric has been found with these glucosaminecompounds. Its use in softening composition is not disclosed.

A further solution is described in Chemical release control, Kamogawa etAl., J. Poly. Sci. . Polym. Chem. Ed. Vol 20, 3121 (1982) which describethe use of amino styrene compounds condensed with aldehydes perfumes,whereby the release of the perfume is triggered by means ofcopolymerisation or acidification of the compound. Its application ishowever not mentioned.

The Applicant has now found that a reaction product between a specificprimary and/or secondary amine and an active component also fulfill sucha need.

Another advantage of the compounds of the invention is their ease ofmanufacture rendering their use most desirable.

SUMMARY OF THE INVENTION

The present invention relates to product of reaction between a primaryand/or secondary amine compound and an active component selected fromketone, aldehyde, and mixtures thereof, characterised in that said aminecompound has an Odor Intensity Index of less than that of a 1% solutionof methylanthranilate in dipropylene glycol, Dry Surface Odor Index ofmore than 5; and with the proviso that said amine compound is not anaminostyrene.

In another aspect of the invention, there is provided a softeningcomposition comprising a primary and/or secondary amine compound and anactive component selected from ketone, aldehyde, and mixtures thereof,characterised in that said amine compound has an Odor Intensity Index ofless than that of a 1% solution of methylanthranilate in dipropyleneglycol.

In a further aspect of the invention, there is provided a method ofdelivering residual fragrance to a surface which comprises the steps ofcontacting said surface with a compound or composition of the inventionand thereafter contacting the treated fabric with a material so that theactive is released from the reaction product between the amine and theactive.

DETAILED DESCRIPTION OF THE INVENTION

The essential component of the invention is the product of reactionbetween a primary and/or secondary amine compound and an activecomponent selected from ketone, aldehyde, and mixtures thereof,characterised in that said amine compound has an Odor Intensity Index ofless than that of a 1% solution of methylanthranilate in dipropyleneglycol, Dry Surface Odor Index of more than 5; and with the proviso thatsaid amine compound is not an aminostyrene.

When incorporated in softening compositions, the amine reaction productis a product of reaction between a primary and/or secondary aminecompound and an active component selected from ketone, aldehyde, andmixtures thereof, characterised in that said amine compound has an OdorIntensity Index of less than that of a 1% solution of methylanthranilatein dipropylene glycol.

Preferably, this compound has a Dry Surface Odor Index of more than 5.

I-Product of Reaction Between a Compound Containing a Primary and/orSecondary Amine Functional Group and a Perfume Component

An essential component of the invention is a product of reaction betweena compound containing a primary and/or secondary amine functional groupand a perfume component, so called hereinafter “amine reaction product”.

A-Primary and/or Secondary Amine

By “primary and/or secondary amine”, it is meant a compound whichcarries at least one primary and/or secondary amine and/or amidefunction.

The primary and/or secondary amine compound is also characterized by anOdor Intensity Index of less than that of a 1% solution ofmethylanthranilate in dipropylene glycol.

Odor Intensity Index Method

By Odor Intensity Index, it meant that the pure chemicals were dilutedat 1% in Dipropylene Glycol, odor-free solvent used in perfumery. Thispercentage is more representative of usage levels. Smelling strips, orso called “blotters”, were dipped and presented to the expert panellistfor evaluation. Expert panellists are assessors trained for at least sixmonths in odor grading and whose gradings are checked for accuracy andreproducibility versus a reference on an on-going basis. For each aminecompound, the panellist was presented two blotters: one reference (MeAnthranilate, unknown from the panellist) and the sample. The panellistwas asked to rank both smelling strips on the 0-5 odor intensity scale,0 being no odor detected, 5 being very strong odor present.

Results

The following represents the Odor Intensity Index of an amine compoundsuitable for use in the present invention and according to the aboveprocedure. In each case, numbers are arithmetic averages among 5 expertpanellists and the results are statistically significantly different at95% confidence level:

Methylanthranilate 1% (reference) 3.4

Ethyl-4-aminobenzoate (EAB) 1% 0.9

A general structure for the primary amine compound of the invention isas follows:

B—(NH2)_(n);

wherein B is a carrier material, and n is an index of value of at least1.

Compounds containing a secondary amine group have a structure similar tothe above excepted that the compound comprises one or more —NH— groupsinstead of —NH2. Further, the compound structure may also have one ormore of both —NH2 and —NH— groups.

Preferred B carriers are inorganic or organic carriers.

By “inorganic carrier”, it is meant a carrier which is non-orsubstantially non carbon based backbones.

Among the inorganic carriers, preferred inorganic carriers are mono orpolymers or organic-organosilicon copolymers of amino derivatised organosilane, siloxane, silazane, alumane, aluminum siloxane, or aluminumsilicate compounds. Typical examples of such carriers are:organosiloxanes with at least one primary amine moiety like thediaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the organoaminosilane (C6H5)3SiNH2 described in: Chemistry and Technology of Silicone, W. Noll,Academic Press Inc. 1998, London, pp 209, 106).

Mono or polymer or organic-organosilicon copolymers containing one ormore organosilylhydrasine moiety are also preferred. A typical exampleof such a class of carrier material is theN,N′-bis(trimethylsilyl)hydrazine (Me3Si) 2NNH2 described in: TheOrganoSilicon Chemistry Second international Symposium, Pure and AppliedChemistry, Vol, 19 Nos 3-4, (1969).

The following are also preferred mono or poly silazanes and which areexemplified by the1,1,1,3,3,3,-hexamethyl-2-phenyidiaminosilyldisilasane [(CH3) 3Si]2NSi(C6H5)NH2) 2 described in: OrganoSilicon Compounds, 1965, V. Bazantand al. Academic Press). Still other preferred examples of polymersilicone derivatives are the cyclic1,1,5,5,7,7,711,11-Octamethyl-3-9-bis-[2-(2-aminoethylamino)-ethyl]-1,5,7,11-tetrasila-3,9-diaza-6,12-dioxacyclododecaneand the Hexaethoxydiamino cyclotetrasiloxane (C6H5) (NH2) 2Si4O4, id,Vol 2 part 2, p 474, p454).

Preferred amino functionalized inorganic polymeric carriers for useherein are polyaminoalkyl polysiloxanes. Typical disclosure can be foundin JP 79,131,096, and EP 058 493. Still other inorganic polymericcarriers suitable for use herein are the amino functionalizedpolydi-alkylsiloxanes, as described in EP 150 867 and having the generalformula:

Wherein R═C₁₋₁₆ preferentially C₁₋₄ alkyl; n is an integer from 0 to 16preferentially from 1 to 6, R′=nil, O, C═O, COO, NC═O, C═O—NR, NR,SO_(m), m=2,3.

By organic carriers, it meant carriers having essentially carbon bondbackbones. Typical amines having organic carrier include aminoarylderivatives, polyamines, aminoacids and derivatives, substituted aminesand amides, glucamines, dendrimers and amino-substitued mono-, di-,oligo-, poly-saccharides.

Of course, the amine compound can be interrupted or substituted bylinkers or cellulose substantive group. A general formula for this aminecompound may be represented as follows:

NH2_(n)—L_(m)—B—L_(m)—R*_(m);

wherein each m is an index of value 0 or at least 1, and n is an indexof value of at least 1 as defined herein before. As can be seen above,the amine group is linked to a carrier molecule as defined by classeshereinafter described. The primary and/or secondary amine group iseither directly linked to the carrier group or via a linker group L. Thecarrier can also be substituted by a R* substituent, and R* can belinked to the carrier either directly or via a linker group L. Ofcourse, R* can also contain branching groups like e.g. tertiary amineand amide groups.

It is important for the purpose of the invention that the amine compoundcomprises at least one primary and/or secondary amine group to reactwith the perfume aldehyde and/or ketone to form the reaction products.Of course, the amine compound is not limited to having only one aminefunction. Indeed, more preferably, the amine compound comprises morethan one amine function, thereby enabling the amine compound to reactwith several aldehydes and/or ketones. Accordingly, reaction productscarrying mixed aldehyde(s) and/or ketone(s) can be achieved, therebyresulting in a mixed release of such fragrances.

Typical linker group include:

L can also contain —O— if this group is not directly linked to N

e.g. H₂N—CH₂—CH₂—O

Most of the compounds described in the classes of amine compoundshereinafter will contain at least one substituent group classified asR*.

R* contains 1 to 22 carbon atoms in the main chain and optionally can bean alkyl, alkenyl, or alkylbenzene chain. It can also contain alicyclic,aromatic, heteroaromatic or heterocyclic systems, either inserted intothe main chain or by substitution of an H atom of the main chain.Further, R* can either be linked to the carrier B material or via alinker L, as defined herein before. In this instance, L can also be —O—.

The main chain can contain from 1 to up to 15 R* groups.

Typical R* insertion groups include:

R* can also contain several insertion groups linked together: e.g.

Furthermore, R* can carry a functional end group E that providesadditional surface substantivity. Typical organic groups of this endgroup E include

E can also be an aromatic, alicyclic, heteroaromatic, or heterocyclicgroup including mono-, di-, oligo-, polysaccharides

In addition, the R* group can also be modified via substitution of oneor more H atoms in the main chain. The substitution group can either beE or the insertion groups as defined above where the insertion group isterminated by any of H, E, or R*.

R* can also be a group made of ethoxy or epoxy groups with n rangingfrom 1 to 15, including groups like:

 —(CH₂CH₂O)_(n)H—(O—CH₂CH₂)_(n)—OH

—(C₃H₆O)_(n)—H—(O—C₃H₆)_(n)—OH

As defined herein before, preferred amine having organic carriermaterial B may be selected from aminoaryl derivatives, polyamines,aminoacids and derivatives, substituted amines and amides, glucamines,amino-substituted mono-, di-, oligo-, poly-saccharides, dendrimersand/or mixtures thereof.

1-Amino Aryl Derivatives

In this class of compounds, the amino group is preferably attached to abenzene ring. The benzene ring is further substituted in the para-and/or meta-position with R* as defined herein before. R* can beattached to the benzene ring via a linker L. The benzene ring can besubstituted by other aromatic ring systems including naphtalene, indole,benzimidazole, pyrimidine, purine, and mixtures thereof.

Preferably, the R* is attached to the benzene ring in its para position.

Typical amino-benzene derivatives have the following formula:

Preferred amino-benzene derivatives have the following formula:

Preferred amino-benzene derivatives are alkyl esters of 4-amino benzoatecompounds, preferably selected from ethyl-4-amino benzoate,phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate,4-amino-N′-(3-aminopropyl)-benzamide, and mixtures thereof.

2-Polyamines

The polyamines of the invention need to have at least one, preferablymore than one free and unmodified primary and/or secondary amine group,to react with the active aldehyde or ketone. In the polyamines, H can besubstituted by R*, optionally via a linker group L. Additionally, theprimary and/or secondary amine group can be linked to the polymer endvia a linker group L.

The polyamines compounds suitable for use in the present invention arewater-soluble or dispersible, polyamines. Typically, the polyamines foruse herein have a molecular weight between 150 and 2*10⁶, preferablybetween 400 and 10⁶, most preferably between 5000 and 10⁶. Thesepolyamines comprise backbones that can be either linear or cyclic. Thepolyamine backbones can also comprise polyamine branching chains to agreater or lesser degree. Preferably, the polyamine backbones describedherein are modified in such a manner that at least one, preferably eachnitrogen of the polyamine chain is thereafter described in terms of aunit that is substituted, quaternized, oxidized, or combinationsthereof.

For the purposes of the present invention the term “modification” as itrelates to the chemical structure of the polyamines is defined asreplacing a backbone —NH hydrogen atom by an R′ unit (substitution),quaternizing a backbone nitrogen (quaternized) or oxidizing a backbonenitrogen to the N-oxide (oxidized). The terms “modification” and“substitution” are used interchangeably when referring to the process ofreplacing a hydrogen atom attached to a backbone nitrogen with an R′unit. Quaternization or oxidation may take place in some circumstanceswithout substitution, but substitution is preferably accompanied byoxidation or quatemization of at least one backbone nitrogen.

The linear or non-cyclic polyamine backbones that comprise the polyaminehave the general formula:

The cyclic polyamine backbones that comprise the polyamine have thegeneral formula:

The above backbones prior to optional but preferred subsequentmodification, comprise primary, secondary and tertiary amine nitrogensconnected by R “linking” units.

For the purpose of the present invention, primary amine nitrogenscomprising the backbone or branching chain once modified are defined asV or Z “terminal” units. For example, when a primary amine moiety,located at the end of the main polyamine backbone or branching chainhaving the structure

H2N—[R]—

is modified according to the present invention, it is thereafter definedas a V “terminal” unit, or simply a V unit. However, for the purposes ofthe present invention, some or all of the primary amine moieties canremain unmodified subject to the restrictions further described hereinbelow. These unmodified primary amine moieties by virtue of theirposition in the backbone chain remain “terminal” units. Likewise, when aprimary amine moiety, located at the end of the main polyamine backbonehaving the structure

—NH2

is modified according to the present invention, it is thereafter definedas a Z “terminal” unit, or simply a Z unit. This unit can remainunmodified subject to the restrictions further described herein below.

In a similar manner, secondary amine nitrogens comprising the backboneor branching chain once modified are defined as W “backbone” units. Forexample, when a secondary amine moiety, the major constituent of thebackbones and branching chains of the present invention, having thestructure

is modified according to the present invention, it is thereafter definedas a W “backbone” unit, or simply a W unit. However, for the purposes ofthe present invention, some or all of the secondary amine moieties canremain unmodified.

These unmodified secondary amine moieties by virtue of their position inthe backbone chain remain “backbone” units.

In a further similar manner, tertiary amine nitrogens comprising thebackbone or branching chain once modified are further referred to as Y“branching” units. For example, when a tertiary amine moiety, which is achain branch point of either the polyamine backbone or other branchingchains or rings, having the structure

is modified according to the present invention, it is thereafter definedas a Y “branching” unit, or simply a Y unit. However, for the purposesof the present invention, some or all or the tertiary amine moieties canremain unmodified. These unmodified tertiary amine moieties by virtue oftheir position in the backbone chain remain “branching” units. The Runits associated with the V, W and Y unit nitrogens which serve toconnect the polyamine nitrogens, are described herein below.

The final modified structure of the polyamines of the present inventioncan be therefore represented by the general formula

V(n+1)WmYnZ

for linear polyamine and by the general formula

V(n−k+1)WmYnY′kZ

for cyclic polyamine. For the case of polyamines comprising rings, a Y′unit of the formula

serves as a branch point for a backbone or branch ring. For every Y′unit there is a Y unit having the formula

that will form the connection point of the ring to the main polymerchain or branch. In the unique case where the backbone is a completering, the polyamine backbone has the formula

therefore comprising no Z terminal unit and having the formula

Vn-kWmYnY′k

wherein k is the number of ring forming branching units. Preferably thepolyamine backbones of the present invention comprise no rings.

In the case of non-cyclic polyamines, the ratio of the index n to theindex m relates to the relative degree of branching. A fullynon-branched linear modified polyamine according to the presentinvention has the formula

VWmZ

that is, n is equal to 0. The greater the value of n (the lower theratio of m to n), the greater the degree of branching in the molecule.Typically the value for m ranges from a minimum value of 2 to 700,preferably 4 to 400, however larger values of m, especially when thevalue of the index n is very low or nearly 0, are also preferred.

Each polyamine nitrogen whether primary, secondary or tertiary, oncemodified according to the present invention, is further defined as beinga member of one of three general classes; simple substituted,quaternized or oxidized. Those polyamine nitrogen units not modified areclassed into V, W Y, Y′ or Z units depending on whether they areprimary, secondary or tertiary nitrogens. That is unmodified primaryamine nitrogens are V or Z units, unmodified secondary amine nitrogensare W units or Y′ units and unmodified tertiary amine nitrogens are Yunits for the purposes of the present invention.

Modified primary amine moieties are defined as V “terminal” units havingone of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Modified secondary amine moieties are defined as W “backbone” unitshaving one of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Other modified secondary amine moieties are defined as Y′ units havingone of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Modified tertiary amine moieties are defined as Y “branching” unitshaving one of three forms:

a) unmodified units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

Certain modified primary amine moieties are defined as Z “terminal”units having one of three forms:

a) simple substituted units having the structure:

b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and

c) oxidized units having the structure:

When any position on a nitrogen is unsubstituted of unmodified, it isunderstood that hydrogen will substitute for R′. For example, a primaryamine unit comprising one R′ unit in the form of a hydroxyethyl moietyis a V terminal unit having the formula (HOCH2CH2)HN—.

For the purposes of the present invention there are two types of chainterminating units, the V and Z units. The Z “terminal” unit derives froma terminal primary amino moiety of the structure —NH2. Non-cyclicpolyamine backbones according to the present invention comprise only oneZ unit whereas cyclic polyamines can comprise no Z units. The Z“terminal” unit can be substituted with any of the R′ units describedfurther herein below, except when the Z unit is modified to form anN-oxide. In the case where the Z unit nitrogen is oxidized to anN-oxide, the nitrogen must be modified and therefore R′ cannot be ahydrogen.

The polyamines of the present invention comprise backbone R “linking”units that serve to connect the nitrogen atoms of the backbone. R unitscomprise units that for the purposes of the present invention arereferred to as “hydrocarbyl R” units and “oxy R” units. The“hydrocarbyl” R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12hydroxyalkylene wherein the hydroxyl moiety may take any position on theR unit chain except the carbon atoms directly connected to the polyaminebackbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxylmoieties may occupy any two of the carbon atoms of the R unit chainexcept those carbon atoms directly connected to the polyamine backbonenitrogens; C8-C12 dialkylarylene which for the purpose of the presentinvention are arylene moieties having two alkyl substituent groups aspart of the linking chain. For example, a dialkylarylene unit has theformula

although the unit need not be 1,4-substituted, but can also be 1,2 or1,3 substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, andmixtures thereof, more preferably ethylene. The “oxy” R units comprise—(R1O)xR5(OR1)x-, —CH2CH(OR2)CH2O)z(R1O)yR1(OCH2CH(OR2)CH2)w-,—CH2CH(OR2)CH2-, —(R1O)xR1-, and mixtures thereof. Preferred R units areselected from the group consisting of C2-C12 alkylene, C3-C12hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene,—(R1O)xR1-, —CH2CH(OR2)CH2-,—(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH—(OH)CH2)w-, —(R1O)xR5(OR1)x-, morepreferred R units are C2-C12 alkylene, C3-C12 hydroxy-alkylene, C4-C12dihydroxyalkylene, —(R1O)xR1-, —(R1O)xR5(OR1)x-, —(CH2CH(OH)CH2)z(R1O)yR1(OCH2CH—(OH)CH2)w-, and mixtures thereof, even more preferred Runits are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures thereof,most preferred are C2-C6 alkylene. The most preferred backbones of thepresent invention comprise at least 50% R units that are ethylene.

R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.R2 is hydrogen, and —(R1O)xB, preferably hydrogen. R3 is C1-C18 alkyl,C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-C12 aryl, andmixtures thereof, preferably C1-C12 alkyl, C7-C12 arylalkylene, morepreferably C1-C12 alkyl, most preferably methyl. R3 units serve as partof R′ units described herein below.

R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10arylene, preferably C1-C10 alkylene, C8-C12 arylalkylene, morepreferably C2-C8 alkylene, most preferably ethylene or butylene.

R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene,C8-C12 dialkylarylene, —C(O)—, —C(O)NHR6NHC(O)—, —C(O)(R4)rC(O)—,—R1(OR1)-, —CH2CH(OH)CH2O(R1O)yR1OCH2CH(OH)CH2-, —C(O)(R4)rC(O)—,—CH2CH(OH)CH2-, R5 is preferably ethylene, —C(O)—, —C(O)NHR6NHC(O)—,—R1(OR1)-, —CH2CH(OH)CH2—, —CH2CH(OH)CH20(R1O)yR1OCH2CH—(OH)CH2-, morepreferably —CH2CH(OH)CH2-. R6 is C2-C12 alkylene or C6-C12 arylene.

The preferred “oxy” R units are further defined in terms of the R1, R2,and R5 units. Preferred “oxy” R units comprise the preferred R1, R2, andR5 units. The preferred polyamines of the present invention comprise atleast 50% RI units that are ethylene. Preferred R1, R2, and R5 units arecombined with the “oxy” R units to yield the preferred “oxy” R units inthe following manner.

i) Substituting more preferred R5 into —(CH2CH2O)xR5(OCH2CH2)x- yields—(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x-.

ii) Substituting preferred R1 and R2 into—(CH2CH(OR2)CH2O)z-(R1O)yR1O(CH2CH(OR2)CH2)w- yields—(CH2CH(OH)CH2O)z-(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w-.

iii) Substituting preferred R2 into —CH2CH(OR2)CH2- yields—CH2CH(OH)CH2-.

R′ units are selected from the group consisting of hydrogen, C1-C22alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl,—(CH2)pCO2M, —(CH2)qSO3M, —CH(CH2CO2M)CO2M, —(CH2)pPO3M, —(R1O)mB,—C(O)R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C1-C22alkylene, —(R1O)mB, —C(O)R3, —(CH2)pCO2M, —(CH2)qSO3M, —CH(CH2CO2M)CO2M,more preferably C1-C22 alkylene, —(R1O)xB, —C(O)R3, —(CH2)pCO2M,—(CH2)qSO3M, —CH(CH2CO2M)CO2M, most preferably C1-C22 alkylene,—(R1O)xB, and —C(O)R3. When no modification or substitution is made on anitrogen then hydrogen atom will remain as the moiety representing R′. Amost preferred R′ unit is (R1O)xB. R′ units do not comprise hydrogenatom when the V, W or Z units are oxidized, that is the nitrogens areN-oxides. For example, the backbone chain or branching chains do notcomprise units of the following structure:

Additionally, R′ units do not comprise carbonyl moieties directly bondedto a nitrogen atom when the V, W or Z units are oxidized, that is, thenitrogens are N-oxides. According to the present invention, the R′ unit—C(O)R3 moiety is not bonded to an N-oxide modified nitrogen, that is,there are no N-oxide amides having the structure

or combinations thereof.

B is hydrogen, C1-C6 alkyl, —(CH2)qSO3M, —(CH2)pCO2M, —(CH2)q-(CHSO3M)CH2SO3M, —(CH2)q(CHSO2M)CH2SO3M, —(CH2)pPO3M, —PO3M, preferablyhydrogen, —(CH2)qSO3M, —(CH2)q(CHSO3M)CH2SO3M, —(CH2)q- (CHSO2M)CH2SO3M,more preferably hydrogen or —(CH2)qSO3M. M is hydrogen or a watersoluble cation in sufficient amount to satisfy charge balance. Forexample, a sodium cation equally satisfies —(CH2)pCO2M, and —(CH2)qSO3M,thereby resulting in —(CH2)pCO2Na, and —(CH2)qSO3Na moieties. More thanone monovalent cation, (sodium, potassium, etc.) can be combined tosatisfy the required chemical charge balance. However, more than oneanionic group may be charge balanced by a divalent cation, or more thanone mono-valent cation may be necessary to satisfy the chargerequirements of a poly-anionic radical. For example, a —(CH2)pPO3Mmoiety substituted with sodium atoms has the formula —(CH2)pPO3Na3.Divalent cations such as calcium (Ca2+) or magnesium (Mg2+) may besubstituted for or combined with other suitable mono-valent watersoluble cations. Preferred cations are sodium and potassium, morepreferred is sodium.

X is a water soluble anion such as chlorine (Cl—), bromine (Br—) andiodine (I—) or X can be any negatively charged radical such as sulfate(SO42-) and methosulfate (CH3SO3-).

The formula indices have the following values: p has the value from 1 to6, q has the value from 0 to 6; r has the value 0 or 1; w has the value0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; zhas the value 0 or 1; m has the value from 2 to 700, preferably from 4to 400, n has the value from 0 to 350, preferably from 0 to 200; m+n hasthe value of at least 5. Preferably x has a value lying in the range offrom 1 to 20, preferably from 1 to 10.

The preferred polyamines of the present invention comprise polyaminebackbones wherein less than 50% of the R groups comprise “oxy” R units,preferably less than 20% , more preferably less than 5%, most preferablythe R units comprise no “oxy” R units.

The most preferred polyamines which comprise no “oxy” R units comprisepolyamine backbones wherein less than 50% of the R groups comprise morethan 3 carbon atoms. For example, ethylene, 1,2-propylene, and1,3-propylene comprise 3 or less carbon atoms and are the preferred“hydrocarbyl” R units. That is when backbone R units are C2-C12alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.

The polyamines of the present invention comprise modified homogeneousand non-homogeneous polyamine backbones, wherein 100% or less of the —NHunits are modified. For the purpose of the present invention the term“homogeneous polyamine backbone” is defined as a polyamine backbonehaving R units that are the same (i.e., all ethylene). However, thissameness definition does not exclude polyamines that comprise otherextraneous units comprising the polymer backbone which are present dueto an artifact of the chosen method of chemical synthesis. For example,it is known to those skilled in the art that ethanolamine may be used asan “initiator” in the synthesis of polyethyleneimines, therefore asample of polyethyleneimine that comprises one hydroxyethyl moietyresulting from the polymerization “initiator” would be considered tocomprise a homogeneous polyamine backbone for the purposes of thepresent invention. A polyamine backbone comprising all ethylene R unitswherein no branching Y units are present is a homogeneous backbone. Apolyamine backbone comprising all ethylene R units is a homogeneousbackbone regardless of the degree of branching or the number of cyclicbranches present.

For the purposes of the present invention the term “non-homogeneouspolymer backbone” refers to polyamine backbones that are a composite ofvarious R unit lengths and R unit types. For example, a non-homogeneousbackbone comprises R units that are a mixture of ethylene and1,2-propylene units. For the purposes of the present invention a mixtureof “hydrocarbyl” and “oxy” R units is not necessary to provide anon-homogeneous backbone.

Preferred polyamines of the present invention comprise homogeneouspolyamine backbones that are totally or partially substituted bypolyethyleneoxy moieties, totally or partially quaternized amines,nitrogens totally or partially oxidized to N-oxides, and mixturesthereof. However, not all backbone amine nitrogens must be modified inthe same manner, the choice of modification being left to the specificneeds of the formulator. The degree of ethoxylation is also determinedby the specific requirements of the formulator.

The preferred polyamines that comprise the backbone of the compounds ofthe present invention are generally polyalkyleneimines (PAI's),preferably polyethyleneimines (PEI's), or PEI's connected by moietieshaving longer R units than the parent PAI's or PEI's.

Preferred amine polymer backbones comprise R units that are C2 alkylene(ethylene) units, also known as polyethylenimines (PEI's). PreferredPEI's have at least moderate branching, that is the ratio of m to n isless than 4:1, however PEI's having a ratio of m to n of 2:1 are mostpreferred. Preferred backbones, prior to modification have the generalformula:

wherein R′, m and n are the same as defined herein above. PreferredPEI's will have a molecular weight greater than 200 daltons.

The relative proportions of primary, secondary and tertiary amine unitsin the polyamine backbone, especially in the case of PEI's, will vary,depending on the manner of preparation. Each hydrogen atom attached toeach nitrogen atom of the polyamine backbone chain represents apotential site for subsequent substitution, quaternization or oxidation.

These polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al.,issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16,1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S.Pat. No. 2,553,696, Wilson, issued May 21, 1951; all herein incorporatedby reference.

Still other polyamines suitable for use in the present invention arepoly[oxy(methyl-1,2-ethanediyl)],α-(2-aminomethylethyl)-ω-(2-aminomethylethoxy)- (=C.A.S. No. 9046-10-0);poly[oxy(methyl-1,2-ethanediyl)], α-hydro-)-ω-(2-aminomethylethoxy)-,ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (=C.A.S. No.39423-51-3); commercially available under the tradename JeffaminesT-403, D-230, D-400, D-2000; 2,2′,2″-triaminotriethylamine;2,2′-diamino-diethylamine; 3,3′-diamino-dipropyl-amine, 1,3 bisaminoethylcyclohexane commercially available from Mitsibushi and the C12Sternamines commercially available from Clariant like the C12Sternamin(propylenamine)_(n) with n=¾, and mixtures thereof.

3-Amino Acids and Derivatives

Still other suitable compounds for use in the present invention areaminoacids and their derivatives, especially ester and amidederivatives. More preferred compounds are those providing enhancedsurface substantivity due to its structural feature. For clarification,the term amino acids and derivatives does not encompass polymericcompounds.

Suitable amino acids have the following functionality of formula:

Wherein R₁=H, R* or (L)—R* and R is the amino acid side group, generallyreferred to as the “R group” such as in “Principles of Biochemistry” byLehninger et al., 1997, Second Edition, Worth, pp114-116.

Preferred amino acids for use herein are selected tyrosine, tryptophane,lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine,phenylalanine, proline, glycine, serine, histidine, threonine,methionine, and mixture thereof, most preferably selected from tyrosine,tryptophane, and mixture thereof. Still other preferred compound are theamino acid derivatives selected from tyrosine ethylate, glycinemethylate, tryptophane ethylate and mixture thereof,

4-Substituted Amines and Amides

For clarification, the term substituted amines and amides does notencompass polymeric compounds. Substituted amine and amide compoundssuitable for use herein have the following general formula:

NH2-L—R**, in which L is —CO— in case of an amide.

Other optional linker group may be as defined under R*.

R** is as defined herein before under R* with the proviso that itcontains at least 6 carbon atoms and/or N atoms and/or cyclohexyl-,piperidine, piperazine, and other heterocyclic groups like:

Optionally, H in NH can be substituted by R*.

Preferred polyamines are polyethyleneimines having the formula:

wherein the value of the indices n and m and the ratios thereof are suchthat they define the following polyamines commercially available underthe tradename Lupasol like Lupasol FG which is characterized by thefollowing: an average molecular weight of about 800 g/mol; a viscosityof 800 mPa at 20° C.; a pour point of about −3° C.; a density at 20° C.of about 1.09 g/mL; and a ratio of primary:secondary:tertiary aminenitrogens of about 1:0.82:0.53; Lupasol 20 wfr which is characterized bythe following: an average molecular weight of about 1300 g/mol; aviscosity of about 5,000 mPa at 20° C.; a pour point of about −16° C.; adensity at 20° C. of about 1.03 g/mL; and a ratio ofprimary:secondary:tertiary amine nitrogens of about 1:0.91:0.64; LupasolPR 8515 which is characterized by the following: an average molecularweight of about 2000 g/mol; a viscosity of from about 300 mPa at 80° C.to about 75,000 mPa at 20° C.; a pour point of about −9° C.; a densityat 20° C. of about 1.05 g/mL; and a ratio of primary:secondary:tertiaryamine nitrogens of about 1:0.92:0.70; Lupasol WF which is characterizedby the following: an average molecular weight of about 25,000 g/mol; aviscosity of from about 2500 mPa at 80° C. to about 200,000 mPa at 20°C.; a pour point of about −3° C.; a density at 20° of about 1.10 g/mL; aratio of primary:secondary:tertiary arnine nitrogens of about1:1.2:0.76; Lupasol FC which is characterized by the following: anaverage molecular weight of about 800 g/mol; a viscosity of about 250mPa at 20° C.; a pour point of about −24° C.; a density at 20° C. ofabout 1.08 g/mL; and a ratio of primary:secondary:tertiary aminenitrogens of about 1:0.86:0.42; Lupasol G20 which is characterized bythe following: an average molecular weight of about 1300 g/mol; aviscosity of about 350 mPa at 20° C.; a pour point of about −24° C.; adensity at 20° C. of about 1.08 g/mL; and a ratio ofprimary:secondary:tertiary amine nitrogens of about 1:0.9:0.64; LupasolG35 which is characterized by the following: an average molecular weightof about 2000 g/mol; a viscosity of about 450 mPa at 20° C.; a pourpoint of about −18° C.; a density at 20° C. of about 1.08 g/mL; and aratio of primary:secondary:tertiary amine nitrogens of about1:0.94:0.67; Lupasol G100 which is characterized by the following: anaverage molecular weight of about 5000 g/mol; a viscosity of about 1200mPa at 20° C.; a pour point of about −18° C.; a density at 20° C. ofabout 1.08 g/mL; and a ratio of primary:secondary:tertiary aminenitrogens of about 1:1.05:0.76; Lupasol HF which is characterized by thefollowing: an average molecular weight of about 25,000 g/mol; aviscosity of about 14,000 mPa at 20° C.; a pour point of about −20° C.;a density at 20° C. of about 1.08 g/mL; and a ratio ofprimary:secondary:tertiary amine nitrogens of about 1:1.2:0.76; LupasolP which is characterized by the following: an average molecular weightof about 750,000 g/mol; a viscosity of from about 1000 mPa at 80° C. toabout 500,000 mPa at 20° C.; a pour point of about −3° C. density at 20°C. of about 1.09 g/mL; and a ratio of primary:secondary:tertiary aminenitrogens of approximately 1:1.07:0.77; Lupasol PS which ischaracterized by the following: an average molecular weight of about750,000 g/mol; a viscosity of about 1400 mPa at 20° C.; a pour point ofabout −5° C.; and a ratio of primary:secondary:tertiary amine nitrogensof about 1:1.07:0.77; Lupasol SK which is characterized by thefollowing: an average molecular weight of about 2,000,000 g/mol; aviscosity of about 750 mPa at 20° C.; a pour point of about 0° C.; and adensity at 20° C. of about 1.06 g/mL; Lupasol SNA which is characterizedby the following: an average molecular weight of about 1,000,000 g/mol;a viscosity of about 500 mPa at 20° C.; a pour point of about 0° C.; anda density at 20° C. of about 1.06 g/mL.

5-Glucamines

Still a further preferred class of amine compound is the class ofglucamines of general structure:

NH2-CH2-(CH(OH))_(x)—CH2OH, wherein one or several OH-function can besubstituted, preferably by —OR*, and wherein x is an integer of value 3or 4. R* can be linked to the OH groups either directly or via linkerunit as mentioned herein before under L.

For clarification, the term glucamine does not encompass polymericcompounds.

Preferred compound of this class are selected from2,3,4,5,6-pentamethoxy- glucamine; 6-acetylglucamine, glucamine, andmixture thereof.

6-Dendrimers

Another further class of amine compounds is the class of dendrimers.Suitable dendrimers carry free primary and/or secondary amine groups atthe periphery of the spherical molecules, that can be reacted with(perfume) aldehydes or ketones to form the desired amine reactionproduct (perfume component) of the invention.

By dendrimers it is understood that the molecule is built up from a coremolecule as described e.g. in WO 96/02588 and in Synthesis, February1978, p. 155-158 or in Encyclopedia of Polymer Science & Engineering,2nd ed., Hedstrand et al., in particular pages 46-91. The core istypically connected to multifunctional components to build up the“generations”. For the purpose of the present invention, the nature ofthe inner generations is not critical. They can be based on e.g.polyamidoamines, polyamidoalcohols, polyethers, polyamides,polyethylenimines, etc. Important for the purpose of the presentinvention is that the outer generation(s) contain accessible primaryand/or secondary amino functions.

Also suitable are the glyco dendrimers as described in e.g. Nachrichtenaus Chemie 11 (1996), p. 1073-1079 and in WO 97/48711 provided that freeprimary and/or secondary amine groups are present at the surface ofthese molecules.

Preferred compounds are the polyethylenimine and polypropyleniminedendrimers, the commercially available Starburst® polyamidoamines(PAMAM) dendrimers, generation G0-G10 from Dendritech and the dendrimersAstromols®, generation 1-5 from DSM being DiAminoButane PolyAmine DAB(PA)x with x=2^(n)×4 and n being generally comprised between 0 and 4.

7-Amino-substituted Mono-, Di-, Oligo-, Poly-saccharides

Also suitable for the purpose of the present invention are specificamino-substituted mono-, di-, oligo-, poly-saccharides.

For the amino-substituted mono-saccharides of the present invention itis necessary that the hemi-acetal and/or hemi-ketal functionality isblocked via a suitable substituent to provide sufficient stability forthe intended application. As indicated here above, glucoseamine is not asuitable amine. However, if the hemi-acetal OH function is substitutedby R*, said monosaccharide becomes suitable for the purpose of thepresent invention. The amino group can be in position 2 to 5 or 6depending on the type of monosaccharide and is preferably in C2, C5 orC6 position. Suitable amino-substituted mono-saccharides are:

C5 aldosen/ketosen: ribose, arabinose, xylose, lyxose, ribulose,xylulose;

C6 aldosen/ketosen: allose, altrose, glucose, mannose, gulose, idose,galactose, talose, fructose, sorbose, tagatose, psicose.

For amino-substituted di-saccharides with non-substituted aldose orketose groups, the free OH-group needs to be substituted by R*, e.g. inlactose and maltose, whereas in sucrose there is no free acetal/ketal OHgroup. Optionally, more than one OH group can be substituted by R*.Suitable amino-substituted di-saccharides are amino substituted lactose,maltose, sucrose, cellobiose and trehalose.

Suitable amino-substituted oligo-, poly-saccharides areamino-substituted starch, cyclodextrin, dextran, glycogen, cellulose,mannan, gueran, levan, alternan glucose, mannose, galactose, fructose,lactose, maltose, sucrose, cellobiose, cyclodextrin, chitosan, and/ormixtures thereof. The molecules need to carry at least 1, preferablyseveral, amino groups. Chitosan does not require additional aminosubstitution.

Also suitable for coupling carboxyl- or aldehyde-containing compoundsare the following functionalised oligo-, poly-saccharides & glycanscommercially available from the company Carbomer. Please find inbrackets the reference number from Carbomer:

Amino alginate (5,00002), Diamino alginate (5,00003), Hexanediaminealginate (5,00004-5,00006-5,00008), dodecanediamine alginate(5,00005-5,00007-5,00009), 6-amino-6-deoxy cellulose (5,00020),O-ethylamine cellulose (5,00022), O-methylamine cellulose (5,00023),3-amino-3-deoxy cellulose (5,00024), 2-amino-2 deoxy cellulose(5,00025), 2,3-diamino-2,3-dideoxy cellulose (5,00026),6-[N-(1,6-hexanediamine)]-6-deoxy cellulose (5,00027),6-[N-(1,12-docedanediamine)]-6-deoxy cellulose (5,00028),O-[methyl-(N-1,6-hexanediamine)] cellulose (5,00029),O-[methyl-(N-1,12-dodecanediamine)] cellulose (5,00030),2,3-di-[N-(1,12-dodecanediamine)] cellulose (5,00031),2,3-diamino-2,3-deoxy alpha-cyclodextrin (5,00050),2,3-diamino-2,3-deoxy beta-cyclodextrin (5,00051), 2,3-diamino-2,3-deoxygamma-cyclodextrin (5,00052), 6-amino-6-deoxy alpha-cyclodextrin(5,00053), 6-amino-6-deoxy beta-cyclodextrin (5,00054), O-ethyleaminobeta-cyclodextrin (5,00055), 6[N-(1,6-hexanediamino)-6-deoxy alphacyclodextrin (5,00056), 6[N-(1,6-hexanediamino)-6-deoxy betacyclodextrin (5,00057), Amino dextran (5,00060),N-[di-(1,6-hexanediamine)] dextran (5,00061),N-[di-(1,12-dodecanediamine)] dextran (5,00062),6-amino-6-deoxy-alpha-D-galactosyl-guaran (5,00070), O-ethylamino guaran(5,00071), Diamino guaran (5,00072), 6-amino-6-deoxy-starch (5,00080),O-ethylamino starch (5,00081), 2,3-diamine-2,3-dideoxy starch (5,00082),N-[6-(1,6-hexanediamine)]-6-deoxy starch (5,00083),N-[6-(1,12-dodecanediamine)]-6-deoxy starch (5,00084) and2,3-di-[N(1,6-hexanediamine)]-2,3-dideoxy starch (5,00085)

Furthermore, with the use of some of the above compound comprising atleast one primary and/or secondary amine group like the polyamine, theresulting amine reaction product will beneficially provide fabricappearance benefits, in particular color care and protection againstfabric wear. Indeed, the appearance of fabrics, e.g., clothing, bedding,household fabrics like table linens is one of the area of concern toconsumers. Indeed, upon typical consumer's uses of the fabrics such aswearing, washing, rinsing and/or tumble-drying of fabrics, a loss in thefabric appearance; which can be at least partly due to loss of colorfidelity and color definition, is observed. Such a problem of color lossis even more acute after multiwash cycles. It has been found that thecompositions of the present invention provide improved fabric appearanceand protection against fabric wear and improved color care to launderedfabrics, especially after multiwash cycles.

Therefore, the compositions of the present invention can providesimultaneously fabric care and long lasting perfume benefits.

B-Active Ketone and/or Aldehyde

Preferably, for the above mentioned compounds, by active ketone oractive aldehyde, it is meant any chain containing at least 1 carbonatom, preferably at least 5 carbon atoms.

Preferably, the active ketone or active aldehyde is respectivelyselected from a flavour ketone or aldehyde ingredient, a pharmaceuticalketone or aldehyde active, a biocontrol ketone or aldehyde agent, aperfume ketone or aldehyde component, a refreshing cooling ketone oraldehyde agent and mixtures thereof.

Flavour ingredients include spices, flavor enhancers that contribute tothe overall flavour perception.

Pharmaceutical actives include drugs.

Biocontrol agents include biocides, antimicrobials, bactericides,fungicides, algaecides, mildewcides, disinfectants, antiseptics,insecticides, vermicides, plant growth hormones.

Biocontrol agents include biocides, antimicrobials, bactericides,fungicides, algaecides, mildewcides, disinfectants, sanitiser likebleach, antiseptics, insecticides, insect and/or moth repellant,vermicides, plant growth hormones.

Typical antimicrobials include Glutaraldehyde, Cinnamaldehyde, andmixtures thereof. Typical insect and/or moth repellants are perfumeingredients, such as citronelial, citral, N, N diethyl meta toluamide,Rotundial, 8-acetoxycarvotanacenone, and mixtures thereof. Otherexamples of insect and/or moth repellant for use herein are disclosed inU.S. Pat. Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660,5,196,200, and “Semio Activity of Flavor and Fragrance molecules onvarious Insect Species”, B. D. Mookherjee et al., published in BioactiveVolatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi,R. G. Buttery, and H. Sugisawa, 1993, pp. 35-48.

A typical disclosure of suitable ketone and/or aldehydes, traditionallyused in perfumery, can be found in “perfume and Flavor Chemicals”, Vol.I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.

Perfume ketones components include components having odoriferousproperties.

Preferably, for the above mentioned compounds, the perfume ketone isselected for its odor character from buccoxime; iso jasmone; methyl betanaphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone,Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose,Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone,Alpha-Ionone, Beta-Ionone, Gamma-Methyl so-called Ionone, Fleuramone,Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl-ketone orMethyl-Cedrylone, Acetophenone, Methyl-Acetophenone,Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone,Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone,6-Isopropyidecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe,4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone,2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone,1-(p-Menthen-6(2)-yl)-1-propanone,4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,2-Acetyl-3,3-Dimethyl-Norbornane,6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinylor Cassione, Gelsone, Hexalon, Isocyclemone E, Methyl Cyclocitrone,Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone,Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone,2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran.

Preferably, for the above mentioned compounds, the preferred ketones areselected from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone,Gamma-Methyl-Ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one,Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate,methyl cedrylone, and mixtures thereof.

Perfume aldehyde components include components having odoriferousproperties.

Preferably, for the above mentioned compounds, the perfume aldehyde isselected for its odor character from adoxal; anisic aldehyde; cymal;ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal;koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T.bucinal; phenyl acetaldehyde; undecylenic aldehyde; vanillin;2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamicaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tertbutylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal,2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal,3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy]acetaldehyde,4-isopropylbenzyaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde,2,6-dimethyl-5-heptenal,4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal,octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde,alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde,m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde,7-hydroxy-3,7-dimethyl octanal, Undecenal,2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde,4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,2,4-dimethyl cyclohexene-3-carbox-aldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al,2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal,2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal,dihydrocinnamic aldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclo-hexene-1-carboxaldehyde, 5 or 6methoxyohexahydro-4,7-methanoindan-1 or 2-carboxaldehyde,3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,4-hydroxy-3-methoxy benzaldehyde,1-methyl-3-(4-methylpentyl)-3-cyclhexene-carboxaldehyde,7-hydroxy-3,7-dimethyl-octanal, trans4-decenal, 2,6-nonadienal,para-tolylacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde,5,9-dimethyl-4,8-decadienal, peony aldehyde(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),hexahydro4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal,alpha-methyl-4-(1-methyl ethyl) benzene acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal,Hexahydro-8,8-dimethyl-2-naphthaldehyde,3-propyl-bicyclo[2.2.1]hept-5-ene-2-carbaldehyde, 9-decenal,3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde, hexanal,trans-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.

Most preferred aldehydes are selected from 1-decanal, benzaldehyde,florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin;2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal;alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T.Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal,trans-2-hexenal, and mixture thereof.

In the above list of perfume ingredients, some are commercial namesconventionally known to one skilled in the art, and also includesisomers. Such isomers are also suitable for use in the presentinvention.

In another embodiment, especially suitable for the purpose of thepresent invention are the perfume compounds, preferably the perfumeketones or active aldehydes, characterised by having a low OdorDetection Threshold. Such Odor Detection Threshold (ODT) should be lowerthan or equal to 1 ppm, preferably lower than or equal to 10ppb—measured at controlled Gas Chromatography (GC) conditions such asdescribed here below. This parameter refers to the value commonly usedin the perfumery arts and which is the lowest concentration at whichsignificant detection takes place that some odorous material is present.Please refer for example in “Compilation of Odor and Taste ThresholdValue Data (ASTM DS 48 A)”, edited by F. A. Fazzalari, InternationalBusiness Machines, Hopwell Junction, N.Y. and in Calkin et al.,Perfumery, Practice and Principles, John Willey & Sons, Inc., page 243et seq (1994). For the purpose of the present invention, the OdorDetection Threshold is measured according to the following method: Thegas chromatograph is characterized to determine the exact volume ofmaterial injected by the syringe, the precise split ratio, and thehydrocarbon response using a hydrocarbon standard of known concentrationand chain-length distribution. The air flow rate is accurately measuredand, assuming the duration of a human inhalation to last 0.02 minutes,the sampled volume is calculated. Since the precise concentration at thedetector at any point in time is known, the mass per volume inhaled isknown and hence the concentration of material. To determine the ODT of aperfume material, solutions are delivered to the sniff port at theback-calculated concentration. A panelist sniffs the GC effluent andidentifies the retention time when odor is noticed. The average over allpanelists determines the threshold of noticeability. The necessaryamount of analyte is injected onto the column to achieve a certainconcentration, such as 10 ppb, at the detector. Typical gaschromatograph parameters for determining odor detection thresholds arelisted below.

GC: 5890 Series II with FID detector

7673 Autosampler

Column: J & W Scientific DB-1

Length 30 meters ID 0.25 mm film thickness 1 micron

Method:

Split Injection: 17/1 split ratio

Autosampler: 1.13 microliters per injection

Column Flow: 1.10 mL/minute

Air Flow: 345 muminute

Inlet Temp. 245° C.

Detector Temp. 285° C.

Temperature Information

Initial Temperature: 50° C.

Rate: 5 C./minute

Final Temperature: 280° C.

Final Time: 6 minutes

Leading assumptions: 0.02 minutes per sniff

GC air adds to sample dilution

Examples of such preferred perfume components are those selected from:2-methyl-2-(para-iso-propylphenyl)-propionaldehyde,1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/orpara-methoxy-acetophenone. Even more preferred are the followingcompounds having an ODT≦10 ppb measured with the method described above:undecylenic aldehyde, undecalactone gamma, heliotropin, dodecalactonegamma, p-anisic aldehyde, para hydroxy-phenyl-butanone, cymal, benzylacetone, ionone alpha, p.t.bucinal, damascenone, ionone beta andmethyl-nonyl ketone.

Typically the level of active is of from 10 to 90%, preferably from 30to 85%, more preferably from 45 to 80% by weight of the amine reactionproduct.

Preferred amine reaction products are those resulting from the reactionof polethyleneimine polymer like Lupasol polymers, with one or more ofthe following Alpha Damascone, Delta Damascone, Carvone, Hedione,Florhydral, Lilial, Heliotropine, Gamma-Methyl-Ionone and2,4-dimethyl-3-cyclohexen-1-carboxaldehyde. Still other preferred aminereaction products are those resulting from the reaction of AstramolDendrimers with Carvone as well as those resulting from the reaction ofethyl-4-amino benzoate with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.

Most preferred amine reaction products are those from the reaction ofLupasol HF with Delta Damascone; LupasolG35 with -Alpha Damascone;LupasolG100 with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,ethyl-4-amino benzoate with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.

Process

Preparation of the component is made as follows in the SynthesisExamples. In general, the nitrogen analogs of ketones and aldehydes arecalled azomethines, Schiff bases or the more preferred name imines.These imines can easily be prepared by condensation of primary aminesand carbonyl compounds by elimination of water.

A typical reaction profile is as follows:

α,β-Unsaturated ketones do not only condense with amines to form imines,but can also undergo a competitive 1,4-addition to form β-aminoketones.

By means of this simple method, compound and composition containing saidcompounds are made which achieve a delayed release of the activeingredient.

As can be observed, the perfume ingredient is typically present inequimolar amount to the amine function so as to enable the reaction totake place and provide the resulting amine reaction product. Of course,higher amount are not excluded and even preferred when the aminecompound comprises more than one amine function. When the amine compoundhas more than one free primary and/or secondary amine function, severaldifferent perfume raw materials can be linked to the amine compound.

Mechanism of Release

By the present invention, a delayed release of a perfume ingredient,i.e. ketone or aldehyde is obtained. Not to be bound by theory, therelease is believed to occur by the following mechanisms:

For imine compounds, the perfume components are released upon breakingdown of the imine bond, leading to the release of the perfume componentand of the primary amine compound. This can be achieved by eitherhydrolysis, photochemical cleavage, oxidative cleavage, or enzymaticcleavage.

For β-aminoketone compounds, treatment with air moisture and/or watersuccessfully releases the perfume component and the amine compound.However, other means of release are not excluded like hydrolysis,photochemical cleavage, oxidative cleavage, or enzymatic cleavage.

Still other means of release for imine as well as β-aminoketonecompounds can be considered such as by the steaming step of ironing thetreated fabric, tumble-drying, and/or wearing.

Applications Compositions

The present invention application compositions include compositionswhere there is a need of a delayed release of an active ketone oraldehyde. This includes compositions for use in the rinse such assoftening compositions, personal cleansing such as shower gels,deodorants, bars, shampoos; stand alone compositions such deodorisingcompositions, insecticides, etc . . . Preferred are those compositionswhich result in contacting the compound of the invention with fabric.The composition of the invention are suitable for use in any step of thedomestic treatment, that is a pre- and/or post-treatment composition, asa wash additive, as a composition suitable for use in the rinse process.Obviously, multiple applications can be made such as treating the fabricwith a pre-treatment composition of the invention and thereafter withthe composition suitable for use in the rinse process and/or dryingprocess.

By compositions suitable for use in the rinse process, these are to beunderstood to include compositions such as rinse added fabric softenercompositions and dryer added compositions (e.g. sheets) which providesoftening and/or antistatic benefits, as well as rinse additives.

Preferred are those compositions which result in contacting the compoundof the invention with fabric. These are to be understood to includecompositions such as rinse added fabric softener compositions and dryeradded compositions (e.g. sheets) which provide softening and/orantistatic benefits.

Preferably, the amine reaction product(s) which is incorporated intosuch compositions provides a dry surface Odor Index of more than 5preferably at least 10.

By Dry Surface Odor Index, it is meant that the amine reactionproduct(s) provides a Delta of more than 5, wherein Delta is thedifference between the Odor Index of the dry surface treated with aminereaction product(s) and of the Odor Index of the dry surface treatedwith only the perfume raw material.

Measurement Method of Dry Surface Odor Index for Fabric Surface

Product Preparation

The amine reaction product is added to the unperfumed product base.

The unperfumed product base, wherein the abreviations are as definedherein after for the examples, is as follows:

Component % by weight DEQA 19.0 HCI 0.02 PEG 0.6 Silicone 0.01 antifoamElectrolyte 1200 (ppm) Dye (ppm) 50 Water and minors to balance to 100%

Levels of amine reaction product are selected so as to obtain an odorgrade on the dry fabric of at least 20. After careful mixing, by shakingthe container in case of a liquid, with a spatula in case of a powder,the product is allowed to sit for 24 hrs.

Washing Process

The resulting product is added into the washing machine in the dosageand in the dispenser appropriate for its category. The quantitycorresponds to recommended dosages made for the corresponding marketproducts: typically between 70 and 150 g for a detergent powder orliquid via current dosing device like granulette, or ariellette, and 25and 40 ml for a liquid fabric softener. The load is composed of fourbath towels (170 g) using a Miele W830 washing machine at 40° C. shortcycle, water input: 15°Hardness at a temperature of 10-18° C., and fullspin of 1200 rpm.

The same process is applied for the corresponding free perfumeingredient in consideration and is used as the reference. Dosages,fabric loads and washing cycles for the reference and the sample areidentical.

Drying Process

Within two hours after the end of the washing cycle, the spinned butstill wet fabrics are assessed for their odors using the scale mentionedbelow. Afterwards, half of the fabric pieces are hung on a line for 24hr drying, away from any possible contaminations. Unless specified, thisdrying takes place indoor. Ambient conditions are at temperature between18-25 C. and air moisture between 50-80%. The other half is placed in atumble drier and undergoes a full “very dry” cycle, i.e. in a Miele,Novotronic T430 set on program white-extra dry (full cycle). Tumble dryfabrics are also assessed on the next day. Fabrics are then stored inopened aluminum bags in an odor free room, and assessed again after 7days.

Odor Evaluations

Odor is assessed by expert panellists smelling carefully the fabrics. A0-100 scale is used for all fabric odor gradings. The grading scale isas follows:

100=extremely strong perfume odor

75=very strong perfume odor

50=strong odor

40=moderate perfume odor

30=slight perfume odor

20=weak perfume odor

10=very weak perfume odor

0=no odor

A difference of more than 5 grades after 1 day and/or 7 days between theamine reaction product and the perfume raw material is statisticallysignificant. A difference of 10 grades or more after one day and/or 7days represents a step-change. In other words, when a difference ofgrade of more than 5, preferably at least 10 is observed between theamine reaction product and the perfume raw material, after either 1 dayor 7 day or both 1 day and 7 days, it can be concluded that the aminereaction product is suitable for use in the present invention, providedthat the amine compound fulfill the Odor Intensity Index.

The amine reaction product as defined herein before typically iscomprised at from 0.0001% to 10%, preferably from 0.001% to 5%, and morepreferably from 0.01% to 2%, by weight of the composition. Mixtures ofthe compounds may also be used herein.

Incorporation of the amine reaction product in the inventioncompositions can conveniently, if necessary, be carried out byconventional incorporation means, such as by spray-on, encapsulationlike starch encapsulation, e.g. such as described in GB1464616, dryaddition, or by encapsulation in cyclodextrin. Preferably, the aminereaction product is preformed before incorporation into the inventioncompositions. In other words, the perfume component and the aminecompound are first reacted together to obtain the resulting aminereaction product as defined in the present invention and only onceformed incorporated into the invention compositions. By being preformedbefore the incorporation in fully formulated composition, a bettercontrol of the compound being made is obtained. Hence, the interactionwith perfume composition which may be present in fully formulatedcomposition is avoided as well as side reaction that could occur.Further, by such means of incorporation, efficient control of the yieldand purity of the compound is obtained.

Most preferably, when the invention composition comprises a perfume, theamine reaction product is incorporated in the composition separatelyfrom the perfume. By this means, the amine reaction product and itssubsequent perfume release is more controlled.

Typically the invention composition comprises surfactancy ingredientssuch as a fabric softening agent, or a surfactant as describedhereinafter as optional ingredients.

When the compositions comprises a softening agent, the resultingcomposition is a softening composition.

Fabric Softening Agents

A fabric softener component provides softness and antistastic propertiesto the treated fabrics. When used, the fabric softener component willtypically be present at a level sufficient to provide softening andantistatic properties.

Said fabric softening component may be selected from cationic, nonionic,amphoteric or anionic fabric softening component.

Typical of the cationic softening components are the quaternary ammoniumcompounds or amine precursors thereof as defined hereinafter.

A)-Quaternary Ammonium Fabric Softening Active Compound

(1) Preferred quaternary ammonium fabric softening active compound havethe formula

or the formula:

wherein Q is a carbonyl unit having the formula:

each R unit is independently hydrogen, C₁-C₆ alkyl, C₁-C₆ hydroxyalkyl,and mixtures thereof, preferably methyl or hydroxy alkyl; each R¹ unitis independently linear or branched C₁₁-C₂₂ alkyl, linear or branchedC₁₁-C₂₂ alkenyl, and mixtures thereof, R² is hydrogen, C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, and mixtures thereof; X is an anion which iscompatible with fabric softener actives and adjunct ingredients; theindex m is from 1 to 4, preferably 2; the index n is from 1 to 4,preferably 2.

An example of a preferred fabric softener active is a mixture ofquatemized amines having the formula:

wherein R is preferably methyl; R¹ is a linear or branched alkyl oralkenyl chain comprising at least 11 atoms, preferably at least 15atoms. In the above fabric softener example, the unit —O₂CR¹ representsa fatty acyl unit which is typically derived from a triglyceride source.The triglyceride source is preferably derived from tallow, partiallyhydrogenated tallow, lard, partially hydrogenated lard, vegetable oilsand/or partially hydrogenated vegetable oils, such as, canola oil,safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, talloil, rice bran oil, etc. and mixtures of these oils.

The preferred fabric softening actives of the present invention are theDiester and/or Diamide Quaternary Ammonium (DEQA) compounds, thediesters and diamides having the formula:

wherein R, R¹, X, and n are the same as defined herein above forformulae (1) and (2), and Q has the formula:

These preferred fabric softening actives are formed from the reaction ofan amine with a fatty acyl unit to form an amine intermediate having theformula:

wherein R is preferably methyl, Q and R¹ are as defined herein before;followed by quaternization to the final softener active.

Non-limiting examples of preferred amines which are used to form theDEQA fabric softening actives according to the present invention includemethyl bis(2-hydroxyethyl)amine having the formula:

methyl bis(2-hydroxypropyl)amine having the formula:

methyl(3-aminopropyl)(2-hydroxyethyl)amine having the formula:

methyl bis(2-aminoethyl)amine having the formula:

triethanol amine having the formula:

di(2-aminoethyl)ethanolamine having the formula:

The counterion, X⁽⁻⁾ above, can be any softener-compatible anion,preferably the anion of a strong acid, for example, chloride, bromide,methylsulfate, ethylsulfate, sulfate, nitrate and the like, morepreferably chloride or methyl sulfate. The anion can also, but lesspreferably, carry a double charge in which case X⁽⁻⁾ represents half agroup.

Tallow and canola oil are convenient and inexpensive sources of fattyacyl units which are suitable for use in the present invention as R¹units. The following are non-limiting examples of quaternary ammoniumcompounds suitable for use in the compositions of the present invention.The term “tallowyl” as used herein below indicates the R¹ unit isderived from a tallow triglyceride source and is a mixture of fatty acylunits. Likewise, the use of the term canolyl refers to a mixture offatty acyl units derived from canola oil.

TABLE II Fabric Softener Actives N,N-di(tallowyl-oxy-ethyl)-N,N-dimethylammonium chloride; N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammoniumchloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)ammonium chloride; N,N-di(canolyl-oxy-ethyl)-N-methyl,N-(2-hydroxyethyl) ammonium chloride;N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chlorideN,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammoniumchloride; N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammonium chloride;N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethylammonium chloride; N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammoniumchloride; N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammoniumchloride; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammoniumchloride; 1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride;and 1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride, andmixtures of the above actives.

Other examples of quaternay ammoniun softening compounds aremethylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate andmethylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammoniummethylsulfate; these materials are available from Witco Chemical Companyunder the trade names Varisoft® 222 and Varisoft® 110, respectively.

Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethylammonium chloride, where the tallow chains are at least partiallyunsaturated.

The level of unsaturation contained within the tallow, canola, or otherfatty acyl unit chain can be measured by the Iodine Value (IV) of thecorresponding fatty acid, which in the present case should preferably bein the range of from 5 to 100 with two categories of compounds beingdistinguished, having a IV below or above 25.

Indeed, for compounds having the formula:

derived from tallow fatty acids, when the Iodine Value is from 5 to 25,preferably 15 to 20, it has been found that a cis/trans isomer weightratio greater than 30/70, preferably greater than 50/50 and morepreferably greater than 70/30 provides optimal concentrability.

For compounds of this type made from tallow fatty acids having a IodineValue of above 25, the ratio of cis to trans isomers has been found tobe less critical unless very high concentrations are needed.

Other suitable examples of fabric softener actives are derived fromfatty acyl groups wherein the terms “tallowyl” and canolyl” in the aboveexamples are replaced by the terms “cocoyl, palmyl, lauryl, oleyl,ricinoleyl, stearyl, palmityl,” which correspond to the triglyceridesource from which the fatty acyl units are derived. These alternativefatty acyl sources can comprise either fully saturated, or preferably atleast partly unsaturated chains.

As described herein before, R units are preferably methyl, however,suitable fabric softener actives are described by replacing the term“methyl” in the above examples in Table II with the units “ethyl,ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl and t-butyl.

The counter ion, X, in the examples of Table II can be suitably replacedby bromide, methylsulfate, formate, sulfate, nitrate, and mixturesthereof. In fact, the anion, X, is merely present as a counterion of thepositively charged quaternary ammonium compounds. The scope of thisinvention is not considered limited to any particular anion.

For the preceding ester fabric softening agents, the pH of thecompositions herein is an important parameter of the present invention.Indeed, it influences the stability of the quaternary ammonium or amineprecursors compounds, especially in prolonged storage conditions.

The pH, as defined in the present context, is measured in the neatcompositions at 20° C. While these compositions are operable at pH ofless than 6.0, for optimum hydrolytic stability of these compositions,the neat pH, measured in the above-mentioned conditions, must preferablybe in the range of from 2.0 to 5, preferably in the range of 2.5 to 4.5,preferably 2.5 to 3.5. The pH of these compositions herein can beregulated by the addition of a Bronsted acid.

Examples of suitable acids include the inorganic mineral acids,carboxylic acids, in particular the low molecular weight (C₁-C₅)carboxylic acids, and alkylsulfonic acids. Suitable inorganic acidsinclude HCl, H₂SO₄, HNO₃ and H₃PO₄. Suitable organic acids includeformic, acetic, citric, methylsulfonic and ethylsulfonic acid. Preferredacids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid,and benzoic acids.

As used herein, when the diester is specified, it will include themonoester that is normally present in manufacture. For softening, underno/low detergent carry-over laundry conditions the percentage ofmonoester should be as low as possible, preferably no more than 2.5%.However, under high detergent carry-over conditions, some monoester ispreferred. The overall ratios of diester to monoester are from 100:1 to2:1, preferably from 50:1 to 5:1, more preferably from 13:1 to 8:1.Under high detergent carry-over conditions, the di/monoester ratio ispreferably 11:1. The level of monoester present can be controlled in themanufacturing of the softener compound.

Mixtures of actives of formula (1) and (2) may also be prepared.

2)-Still other suitable quaternary ammonium fabric softening compoundsfor use herein are cationic nitrogenous salts having two or more long-chain acyclic aliphatic C₈-C₂₂ hydrocarbon groups or one said group andan arylalkyl group which can be used either alone or as part of amixture are selected from the group consisting of:

(i) acyclic quaternary ammonium salts having the formula:

wherein R⁴ is an acyclic aliphatic C₈-C₂₂ hydrocarbon group, R⁵ is aC₁-C₄ saturated alkyl or hydroxyalkyl group, R⁸ is selected from thegroup consisting of R⁴ and R⁵ groups, and A− is an anion defined asabove;

(ii) diamino alkoxylated quaternary ammonium salts having the formula:

wherein n is equal to 1 to 5, and R¹, R², R⁵ and A⁻ are as definedabove;

(iii) mixtures thereof.

Examples of the above class cationic nitrogenous salts are thewell-known dialkyldi methylammonium salts such asditallowdimethylammonium chloride, ditallowdimethylammoniummethylsulfate, di(hydrogenatedtallow)dimethylammonium chloride,distearyidimethylammonium chloride, dibehenyidimethylammonium chloride.Di(hydrogenatedtallow)di methylammonium chloride andditallowdimethylammonium chloride are preferred. Examples ofcommercially available dialkyldimethyl ammonium salts usable in thepresent invention are di(hydrogenatedtallow)dimethylammonium chloride(trade name Adogen® 442), ditallowdimethylammonium chloride (trade nameAdogen® 470, Praepagen® 3445), distearyl dimethylammonium chloride(trade name Arosurf® TA-100), all available from Witco Chemical Company.Dibehenyidimethylammonium chloride is sold under the trade name KemamineQ-2802C by Humko Chemical Division of Witco Chemical Corporation.

Dimethylstearylbenzyl ammonium chloride is sold under the trade namesVarisoft® SDC by Witco Chemical Company and Ammonyx® 490 by OnyxChemical Company.

B)-Amine Fabric Softening Active Compound

Suitable amine fabric softening compounds for use herein, which may bein amine form or cationic form are selected from:

(i)-Reaction products of higher fatty acids with a polyamine selectedfrom the group consisting of hydroxyalkylalkylenediamines anddialkylenetriamines and mixtures thereof. These reaction products aremixtures of several compounds in view of the multi-functional structureof the polyamines.

The preferred Component (i) is a nitrogenous compound selected from thegroup consisting of the reaction product mixtures or some selectedcomponents of the mixtures.

One preferred component (i) is a compound selected from the groupconsisting of substituted imidazoline compounds having the formula:

wherein R⁷ is an acyclic aliphatic C₁₅-C₂₁ hydrocarbon group and R⁸ is adivalent C₁-C₃ alkylene group.

Component (i) materials are commercially available as: Mazamide® 6, soldby Mazer Chemicals, or Ceranine® HC, sold by Sandoz Colors & Chemicals;stearic hydroxyethyl imidazoline sold under the trade names of Alkazine®ST by Alkaril Chemicals, Inc., or Schercozoline® S by Scher Chemicals,Inc.; N,N″-ditallowalkoyidiethylenetriamine;1-tallowamidoethyl-2-tallowimidazoiine (wherein in the precedingstructure R¹ is an aliphatic C₁₅-C₁₇ hydrocarbon group and R⁸ is adivalent ethylene group).

Certain of the Components (i) can also be first dispersed in a Bronstedacid dispersing aid having a pKa value of not greater than 4; providedthat the pH of the final composition is not greater than 6. Somepreferred dispersing aids are hydrochloric acid, phosphoric acid, ormethylsulfonic acid.

Both N,N″-ditallowalkoyldiethylenetriamine and1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of tallowfatty acids and diethylenetriamine, and are precursors of the cationicfabric softening agent methyl-1-tallowamidoethyl-2-tallowimidazoliniummethylsulfate (see “Cationic Surface Active Agents as Fabric Softeners,”R. R. Egan, Journal of the American Oil Chemicals' Society, January1978, pages 118-121). N,N″-ditallow alkoyldiethylenetriamine and1-tallowamidoethyl-2-tallowimidazoline can be obtained from WitcoChemical Company as experimental chemicals.Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold byWitco Chemical Company under the tradename Varisoft® 475.

(ii)-softener having the formula:

wherein each R² is a C₁₋₆ alkylene group, preferably an ethylene group;and G is an oxygen atom or an —NR— group; and each R, R¹, R² and R⁵ havethe definitions given above and A⁻ has the definitions given above forX⁻.

An example of Compound (ii) is 1-oleylamidoethyl-2-oleylimidazoliniumchloride wherein R¹ is an acyclic aliphatic C₁₅-C₁₇ hydrocarbon group,R² is an ethylene group, G is a NH group, R⁵ is a methyl group and A⁻ isa chloride anion.

(iii)-softener having the formula:

wherein R, R¹, R², and A⁻ are defined as above.

An example of Compound (iii) is the compound having the formula:

wherein R¹ is derived from oleic acid.

Additional fabric softening materials may be used in addition oralternatively to the cationic fabric softener. These may be selectedfrom nonionic, amphoteric or anionic fabric softening material.Disclosure of such materials may be found in U.S. Pat. Nos. 4,327,133;4,421,792; 4,426,299; 4,460,485; 3,644,203; 4,661,269; 4,439,335;3,861,870; 4,308,151; 3,886,075; 4,233,164; 4,401,578; 3,974,076;4,237,016 and EP 472,178.

Typically, such nonionic fabric softener materials have an HLB of from 2to 9, more typically from 3 to 7. Such nonionic fabric softenermaterials tend to be readily dispersed either by themselves, or whencombined with other materials such as single-long-chain alkyl cationicsurfactant described in detail hereinafter. Dispersibility can beimproved by using more single-long-chain alkyl cationic surfactant,mixture with other materials as set forth hereinafter, use of hotterwater, and/or more agitation. In general, the materials selected shouldbe relatively crystalline, higher melting, (e.g. >40° C.) and relativelywater-insoluble.

Preferred nonionic softeners are fatty acid partial esters of polyhydricalcohols, or anhydrides thereof, wherein the alcohol, or anhydride,contains from 2 to 18, preferably from 2 to 8, carbon atoms, and eachfatty acid moiety contains from 12 to 30, preferably from 16 to 20,carbon atoms. Typically, such softeners contain from one to 3,preferably 2 fatty acid groups per molecule.

The polyhydric alcohol portion of the ester can be ethylene glycol,glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol,xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.Sorbitan esters and polyglycerol monostearate are particularlypreferred.

The fatty acid portion of the ester is normally derived from fatty acidshaving from 12 to 30, preferably from 16 to 20, carbon atoms, typicalexamples of said fatty acids being lauric acid, myristic acid, palmiticacid, stearic acid and behenic acid. Highly preferred optional nonionicsoftening agents for use in the present invention are the sorbitanesters, which are esterified dehydration products of sorbitol, and theglycerol esters.

Commercial sorbitan monostearate is a suitable material. Mixtures ofsorbitan stearate and sorbitan palmitate having stearate/palmitateweight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters arealso useful.

Glycerol and polyglycerol esters, especially glycerol, diglycerol,triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-,are preferred herein (e.g. polyglycerol monostearate with a trade nameof Radiasurf 7248).

Useful glycerol and polyglycerol esters include mono-esters withstearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenicacids and the diesters of stearic, oleic, palmitic, lauric, isostearic,behenic, and/or myristic acids. It is understood that the typicalmono-ester contains some di- and tri-ester, etc.

The “glycerol esters” also include the polyglycerol, e.g., diglycerolthrough octaglycerol esters. The polyglycerol polyols are formed bycondensing glycerin or epichlorohydrin together to link the glycerolmoieties via ether linkages. The mono- and/or diesters of thepolyglycerol polyols are preferred, the fatty acyl groups typicallybeing those described herein before for the sorbitan and glycerolesters.

Further fabric softening components suitable for use herein are thesoftening clays, such as the low ion-exchange-capacity ones described inEP-A-0,150,531.

Of course, the term “softening active” can also encompass mixedsoftening active agents.

Preferred among the classes of softener compounds disclosed hereinbefore are the diester or diamido quaternary ammonium fabric softeningactive compound (DEQA).

The fabric softener compounds herein are present at levels of from 1% to80% of compositions herein, depending on the composition execution whichcan be dilute with a preferred level of active from 5% to 15%, orconcentrated, with a preferred level of active from 15% to 50%, mostpreferably 15% to 35% by weight of the composition.

Fully formulated softening compositions preferably contain, in additionto the herein before described components, one or more of the followingingredients.

(A) Brighteners

The compositions herein can also optionally contain from 0.005% to 5% byweight of certain types of hydrophilic optical brighteners which alsoprovide a dye transfer inhibition action. If used, the compositionsherein will preferably comprise from 0.001% to 1% by weight of suchoptical brighteners. The hydrophilic optical brighteners useful in thepresent invention are those having the structural formula:

wherein R₁ is selected from anilino, N-2-bis-hydroxyethyl andNH-2-hydroxyethyl; R₂ is selected from N-2-bis-hydroxyethyl,N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is asalt-forming cation such as sodium or potassium.

When in the above formula, R₁ is anilino, R₂ is N-2-bis-hydroxyethyl andM is a cation such as sodium, the brightener is4,4′,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2′-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-GeigyCorporation. Tinopal-UNPA-GX is the preferred hydrophilic opticalbrightener useful in the rinse added compositions herein.

When in the above formula, R₁ is anilino, R₂ isN-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, thebrightener is4,4′-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid disodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.

When in the above formula, R₁ is anilino, R₂ is morphilino and M is acation such as sodium, the brightener is4,4′-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2′-stilbenedisulfonicacid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.

(B) Dispersibility Aids

Relatively concentrated compositions containing both saturated andunsaturated diester quaternary ammonium compounds can be prepared thatare stable without the addition of concentration aids. However, thecompositions of the present invention may require organic and/orinorganic concentration aids to go to even higher concentrations and/orto meet higher stability standards depending on the other ingredients.These concentration aids which typically can be viscosity modifiers maybe needed, or preferred, for ensuring stability under extreme conditionswhen particular softener active levels are used. The surfactantconcentration aids are typically selected from the group consisting of(1) single long chain alkyl cationic surfactants; (2) nonionicsurfactants; (3) amine oxides; (4) fatty acids; and (5) mixturesthereof. These aids are described in WO 94/20597, specifically on page14, line 12 to page 20, line 12, which is herein incorporated byreference.

When said dispersibility aids are present, the total level is from 2% to25%, preferably from 3% to 17%, more preferably from 4% to 15%, and evenmore preferably from 5% to 13% by weight of the composition. Thesematerials can either be added as part of the active softener rawmaterial, (I), e.g., the mono-long chain alkyl cationic surfactantand/or the fatty acid which are reactants used to form the biodegradablefabric softener active as discussed herein before, or added as aseparate component. The total level of dispersibility aid includes anyamount that may be present as part of component (I).

(1) Mono-Alkyl Cationic Quaternary Ammonium Compound

When the mono-alkyl cationic quaternary ammonium compound is present, itis typically present at a level of from 2% to 25%, preferably from 3% to17%, more preferably from 4% to 15%, and even more preferably from 5% to13% by weight of the composition, the total mono-alkyl cationicquaternary ammonium compound being at least at an effective level.

Such mono-alkyl cationic quaternary ammonium compounds useful in thepresent invention are, preferably, quaternary ammonium salts of thegeneral formula:

[R⁴N⁺(R⁵)₃]X⁻

wherein

R⁴ is C₈-C₂₂ alkyl or alkenyl group, preferably C₁₀-C₁₈ alkyl or alkenylgroup; more preferably C₁₀-C₁₄ or C₁₆-C₁₈ alkyl or alkenyl group;

each R⁵ is a C₁-C₆ alkyl or substituted alkyl group (e.g., hydroxyalkyl), preferably C₁-C₃ alkyl group, e.g., methyl (most preferred),ethyl, propyl, and the like, a benzyl group, hydrogen, a polyethoxylatedchain with from 2 to 20 oxyethylene units, preferably from 2.5 to 13oxyethylene units, more preferably from 3 to 10 oxyethylene units, andmixtures thereof; and

X⁻ is as defined herein before for (Formula (I)).

Especially preferred dispersibility aids are monolauryl trimethylammonium chloride and monotallow trimethyl ammonium chloride availablefrom Witco under the trade names Adogen® 412 and Adogen® 471, monooleylor monocanola trimethyl ammonium chloride available from Witco under thetradename Adogen® 417, monococonut trimethyl ammonium chloride availablefrom Witco under the trade name Adogen® 461, and monosoya trimethylammonium chloride available from Witco under the trade name Adogen® 415.The R⁴ group can also be attached to the cationic nitrogen atom througha group containing one, or more, ester, amide, ether, amine, etc.,linking groups which can be desirable for increased concentratability ofcomponent (I), etc. Such linking groups are preferably within from oneto three carbon atoms of the nitrogen atom.

Mono-alkyl cationic quaternary ammonium compounds also include C₈-C₂₂alkyl choline esters. The preferred dispersibility aids of this typehave the formula:

R¹C(O)—O—CH₂CH₂N⁺(R)₃X⁻

wherein R¹, R and X⁻ are as defined previously.

Highly preferred dispersibility aids include C₁₂-C₁₄ coco choline esterand C₁₆-C₁₈ tallow choline ester.

Suitable biodegradable single-long-chain alkyl dispersibility aidscontaining an ester linkage in the long chains are described in U.S.Pat. No. 4,840,738, said patent being incorporated herein by reference.

When the dispersibility aid comprises alkyl choline esters, preferablythe compositions also contain a small amount, preferably from 2% to 5%by weight of the composition, of organic acid. Organic acids aredescribed in EP404,471, which is herein incorporated by reference.Preferably the organic acid is selected from the group consisting ofglycolic acid, acetic acid, citric acid, and mixtures thereof.

Ethoxylated quaternary ammonium compounds which can serve as thedispersibility aid include ethylbis(polyethoxy ethanol)alkylammoniumethyl-sulfate with 17 moles of ethylene oxide, available under the tradename Variquat® 66 from Witco Corporation; polyethylene glycol (15)oleammonium chloride, available under the trade name Ethoquad® 0/25 fromAkzo; and polyethylene glycol (15) cocomonium chloride, available underthe trade name Ethoquad® C/25 from Akzo.

Quatemary compounds having only a single long alkyl chain, can protectthe cationic softener from interacting with anionic surfactants and/ordetergent builders that are carried over into the rinse from the washsolution.

(2) Nonionic Surfactant (Alkoxylated Materials)

Suitable nonionic surfactants to serve as the viscosity/dispersibilitymodifier include addition products of ethylene oxide and, optionally,propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc.They are referred to herein as ethoxylated fatty alcohols, ethoxylatedfatty acids, and ethoxylated fatty amines. Any of the alkoxylatedmaterials of the particular type described hereinafter can be used asthe nonionic surfactant. In general terms, the nonionics herein, whenused alone, in liquid compositions are at a level of from 0% to 5%,preferably from 0.1% to 5%, more preferably from 0.2% to 3%. Suitablecompounds are substantially water-soluble surfactants of the generalformula:

R²—Y—(C₂H₄O)_(Z)—C₂H₄OH

wherein R² for both solid and liquid compositions is selected from thegroup consisting of primary, secondary and branched chain alkyl and/oracyl hydrocarbyl groups; primary, secondary and branched chain alkenylhydrocarbyl groups; and primary, secondary and branched chain alkyl- andalkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groupshaving a hydrocarbyl chain length of from 8 to 20, preferably from 10 to18 carbon atoms. More preferably the hydrocarbyl chain length for liquidcompositions is from 16 to 18 carbon atoms and for solid compositionsfrom 10 to 14 carbon atoms. In the general formula for the ethoxylatednonionic surfactants herein, Y is typically —O—, —C(O)O—, —C(O)N(R)—, or—C(O)N(R)R—, preferably —O—, and in which R², and R, when present, havethe meanings given herein before, and/or R can be hydrogen, and z is atleast 8, preferably at least 10-11. Performance and, usually, stabilityof the softener composition decrease when fewer ethoxylate groups arepresent.

The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to15. Of course, by defining R² and the number of ethoxylate groups, theHLB of the surfactant is, in general, determined. However, it is to benoted that the nonionic ethoxylated surfactants useful herein, forconcentrated liquid compositions, contain relatively long chain R²groups and are relatively highly ethoxylated. While shorter alkyl chainsurfactants having short ethoxylated groups can possess the requisiteHLB, they are not as effective herein. Nonionic surfactants as theviscosity/dispersibility modifiers are preferred over the othermodifiers disclosed herein for compositions with higher levels ofperfume.

Examples of nonionic surfactants follow. The nonionic surfactants ofthis invention are not limited to these examples. In the examples, theinteger defines the number of ethoxy (EO) groups in the molecule.

(3) Amine Oxides

Suitable amine oxides include those with one alkyl or hydroxyalkylmoiety of 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms,more preferably from 8 to 14 carbon atoms, and two alkyl moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups with 1 to 3 carbon atoms.

Examples include dimethyloctylamine oxide, diethyidecylamine oxide,bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide,dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.

(C) Stabilizers

Stabilizers can be present in the compositions of the present invention.The term “stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% to 2%,preferably from 0.01% to 0.2%, more preferably from 0.035% to 0.1% forantioxidants, and more preferably from 0.01% to 0.2% for reductiveagents. These assure good odor stability under long term storageconditions. Antioxidants and reductive agent stabilizers are especiallycritical for unscented or low scent products (no or low perfume).

Examples of antioxidants that can be added to the compositions of thisinvention include a mixture of ascorbic acid, ascorbic palmitate, propylgallate, available from Eastman Chemical Products, Inc., under the tradenames Tenox® PG and Tenox® S-1; a mixture of BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, andcitric acid, available from Eastman Chemical Products, Inc., under thetrade name Tenox®-6; butylated hydroxytoluene, available from UOPProcess Division under the trade name Sustane® BHT; tertiarybutylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ;natural tocopherols, Eastman Chemical Products, Inc., as TenoxeGT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,Inc., as BHA; long chain esters (C₈-C₂₂) of gallic acid, e.g., dodecylgallate; Irganox® 1010; Irganox® 1035; Irganox® B 1171; Irganox® 1425;Irganox® 3114; Irganox® 3125; and mixtures thereof; preferably Irganox®3125, Irganox® 1425, Irganox® 3114, and mixtures thereof; morepreferably Irganox® 3125 alone or mixed with citric acid and/or otherchelators such as isopropyl citrate, Dequest® 2010, available fromMonsanto with a chemical name of 1-hydroxyethylidene-1,1-diphosphonicacid (etidronic acid), and Tiron®, available from Kodak with a chemicalname of 4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®,available from Aldrich with a chemical name ofdiethylenetriaminepentaacetic acid.

(D) Soil Release Agent

In the present invention, an optional soil release agent can be added.Typical levels of incorporation in the composition are from 0% to 10%,preferably from 0.2% to 5%, of a soil release agent. Preferably, such asoil release agent is a polymer.

Soil Release agents are desirably used in fabric softening compositionsof the instant invention. Any polymeric soil release agent known tothose skilled in the art can optionally be employed in the compositionsof this invention. Polymeric soil release agents are characterized byhaving both hydrophilic segments, to hydrophilize the surface ofhydrophobic fibers, such as polyester and nylon, and hydrophobicsegments, to deposit upon hydrophobic fibers and remain adhered theretothrough completion of washing and rinsing cycles and, thus, serve as ananchor for the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably from about 0.2% toabout 3.0%.

The following, all included herein by reference, describe soil releasepolymers suitable for use in the present invention. U.S. Pat. No.3,959,230 Hays, issued May 25, 1976; U.S. Pat. No. 3,893,929 Basadur,issued Jul. 8, 1975; U.S. Pat. No. 4,000,093, Nicol, et al., issued Dec.28, 1976; U.S. Pat. No. 4,702,857 Gosselink, issued Oct. 27, 1987; U.S.Pat. No. 4,968,451, Scheibel et al., issued November 6; U.S. Pat. No.4,702,857, Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730,Gosselink et al., issued Dec. 8, 1987; U.S. Pat. No. 4,721,580,Gosselink, issued Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado etal., issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al.,issued Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issuedMay 16, 1995; European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al..

Further suitable soil release agents are described in U.S. Pat. No.4,201,824, Violland et al.; U.S. Pat. No. 4,240,918 Lagasse et al.; U.S.Pat. No. 4,525,524 Tung et al.; U.S. Pat. No. 4,579,681, Ruppert et al.;U.S. Pat. No. 4,240,918; U.S. Pat. No. 4,787,989; U.S. Pat. No.4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A toBASF (1991); and DE 2,335,044 to Unilever N. V., 1974 all incorporatedherein by reference.

Commercially available soil release agents include the METOLOSE SM100,METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN typeof material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON5126 (from Dupont) and MILEASE T (from ICI).

(E) Scum Dispersant

In the present invention, the premix can be combined with an optionalscum dispersant, other than the soil release agent, and heated to atemperature at or above the melting point(s) of the components.

The preferred scum dispersants herein are formed by highly ethoxylatinghydrophobic materials. The hydrophobic material can be a fatty alcohol,fatty acid, fatty amine, fatty acid amide, amine oxide, quaternaryammonium compound, or the hydrophobic moieties used to form soil releasepolymers. The preferred scum dispersants are highly ethoxylated, e.g.,more than 17, preferably more than 25, more preferably more than 40,moles of ethylene oxide per molecule on the average, with thepolyethylene oxide portion being from 76% to 97%, preferably from 81% to94%, of the total molecular weight.

The level of scum dispersant is sufficient to keep the scum at anacceptable, preferably unnoticeable to the consumer, level under theconditions of use, but not enough to adversely affect softening. Forsome purposes it is desirable that the scum is nonexistent. Depending onthe amount of anionic or nonionic detergent, etc., used in the washcycle of a typical laundering process, the efficiency of the rinsingsteps prior to the introduction of the compositions herein, and thewater hardness, the amount of anionic or nonionic detergent surfactantand detergency builder (especially phosphates and zeolites) entrapped inthe fabric (laundry) will vary. Normally, the minimum amount of scumdispersant should be used to avoid adversely affecting softeningproperties. Typically scum dispersion requires at least 2%, preferablyat least 4% (at least 6% and preferably at least 10% for maximum scumavoidance) based upon the level of softener active. However, at levelsof 10% (relative to the softener material) or more, one risks loss ofsoftening efficacy of the product especially when the fabrics containhigh proportions of nonionic surfactant which has been absorbed duringthe washing operation.

Preferred scum dispersants are: Brij 700®; Varonic U-250®; GenapolT-500®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.

(F) Bactericides

Examples of bactericides used in the compositions of this inventioninclude glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diolsold by Inolex Chemicals, located in Philadelphia, Pa., under the tradename Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-oneand 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company underthe trade name Kathon 1 to 1,000 ppm by weight of the agent.

(G) Perfume

The present invention can contain any softener compatible perfume.Suitable perfumes are disclosed in U.S. Pat. No. 5,500,138, said patentbeing incorporated herein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

Examples of perfume ingredients useful in the perfumes of the presentinvention compositions include, but are not limited to, hexyl cinnamicaldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate;terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol;2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol;3,7-dimethyl-trans-2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol;3,7-dimethyl-1-octanol;2-methyl-3-(para-tert-butylphenyl)-propion-aldehyde;4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbox-aldehyde;tri-cyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydroxyphenyl)-butan-2-one;1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.

Additional examples of fragrance materials include, but are not limitedto, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil;dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate;beta-naphthol methylether; methyl-beta-naphthylketone; coumarin;decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate;alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate;Schiffs base of4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methylanthranilate; cyclic ethyleneglycol diester of tridecandioic acid;3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl; ionone alpha;ionone beta; petitgrain; methyl cedrylone;7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-ylketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;6-acetyl-1,1,2,3,3,5-hexamethyl indane;5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexylcarboxaldehyde; formyl tricyclodecan; cyclopentadecanolide;16-hydroxy-9-hexadecenoic acid lactone;1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane;ambroxane; dodecahydro-3a,6,6,9a-tetramethyinaphtho-[2,1b]furan; cedrol;5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexylacetate; patchouli; olibanum resinoid; labdanum; vetivert; copaibabalsam; fir balsam; and condensation products of: hydroxycitronellal andmethyl anthranilate; hydroxycitronellal and indol; phenyl acetaldehydeand indol; 4-(4-hydroxy4-methyl pentyl)-3-cyclohexene-1-carboxaldehydeand methyl anthranilate.

More examples of perfume components are geraniol; geranyl acetate;linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellylacetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol;terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethylacetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzylbenzoate; styrallyl acetate; dimethylbenzylcarbinol;trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononylacetate; vetiveryl acetate; vetiverol;2-methyl-3-(p-tert-butylphenyl)-propanal;2-methyl-3-(p-isopropylphenyl)-propanal;3-(p-tert-butylphenyl)-propanal;4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;2-n-heptylcyclopentanone; 3-methyl-2-pentyl- cyclopentanone; n-decanal;n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehydedimethylacetal; phenylacetaldehyde diethylacetal; geranonitrile;citronellonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedrylmethylether; isolongifolanone; aubepine nitrile; aubepine; heliotropine;eugenol; vanillin; diphenyl oxide; hydroxycitronellal ionones; methylionones; isomethyl ionomes; irones; cis-3-hexenol and esters thereof;indane musk fragrances; tetralin musk fragrances; isochroman muskfragrances; macrocyclic ketones; macrolactone musk fragrances; ethylenebrassylate.

The perfumes useful in the present invention compositions aresubstantially free of halogenated materials and nitromusks.

Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

Perfume can be present at a level of from 0% to 10%, preferably from0.1% to 5%, and more preferably from 0.2% to 3%, by weight of thefinished composition. Fabric softener compositions of the presentinvention provide improved fabric perfume deposition.

(H) Chelating Agents

The compositions and processes herein can optionally employ one or morecopper and/or nickel chelating agents (“chelators”). Such water-solublechelating agents can be selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures thereof, all as hereinafter defined. Thewhiteness and/or brightness of fabrics are substantially improved orrestored by such chelating agents and the stability of the materials inthe compositions are improved. Without intending to be bound by theory,it is believed that the benefit of these materials is due in part totheir exceptional ability to remove iron and manganese ions from washingsolutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilo- triacetates, ethylenediamine tetraproprionates,triethylenetetra-aminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methyienephosphonates) as DEQUEST. Preferred,these amino phosphonates do not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixturesthereof.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the fabric care compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

(I) Crystal Growth Inhibitor Component

The compositions of the present invention can further contain a crystalgrowth inhibitor component, preferably an organodiphosphonic acidcomponent, incorporated preferably at a level of from 0.01% to 5%, morepreferably from 0.1% to 2% by weight of the compositions.

By organo diphosphonic acid it is meant herein an organo diphosphonicacid which does not contain nitrogen as part of its chemical structure.This definition therefore excludes the organo aminophosphonates, whichhowever may be included in compositions of the invention as heavy metalion sequestrant components.

The organo diphosphonic acid is preferably a C₁-C₄ diphosphonic acid,more preferably a C₂ diphosphonic acid, such as ethylene diphosphonicacid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP)and may be present in partially or fully ionized form, particularly as asalt or complex.

Still useful herein as crystal growth inhibitor is the organicmonophosphonic acid.

Organo monophosphonic acid or one of its salts or complexes is alsosuitable for use herein as a CGI.

By organo monophosphonic acid it is meant herein an organomonophosphonic acid which does not contain nitrogen as part of itschemical structure. This definition therefore excludes the organoaminophosphonates, which however may be included in compositions of theinvention as heavy metal ion sequestrants.

The organo monophosphonic acid component may be present in its acid formor in the form of one of its salts or complexes with a suitable countercation. Preferably any salts/complexes are water soluble, with thealkali metal and alkaline earth metal salts/complexes being especiallypreferred.

A prefered organo monophosphonic acid is2-phosphonobutane-1,2,4-tricarboxylic acid commercially available fromBayer under the tradename of Bayhibit.

(J)-Enzyme

The compositions and processes herein can optionally employ one or moreenzymes such as lipases, proteases, cellulase, amylases and peroxidases.A preferred enzyme for use herein is a cellulase enzyme. Indeed, thistype of enzyme will further provide a color care benefit to the treatedfabric. Cellulases usable herein include both bacterial and fungaltypes, preferably having a pH optimum between 5 and 9.5. U.S. Pat. No.4,435,307 discloses suitable fungal cellulases from Humicola insolens orHumicola strain DSM1800 or a cellulase 212-producing fungus belonging tothe genus Aeromonas, and cellulase extracted from the hepatopancreas ofa marine mollusk, Dolabella Auricula Solander. Suitable cellulases arealso disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.CAREZYMEO® and CELLUZYME® (Novo) are especially useful. Other suitablecellulases are also disclosed in WO 91/17243 to Novo, WO 96/34092, WO96/34945 and EP-A-0,739,982. In practical terms for current commercialpreparations, typical amounts are up to 5 mg by weight, more typically0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.Stated otherwise, the compositions herein will typically comprise from0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzymepreparation. In the particular cases where activity of the enzymepreparation can be defined otherwise such as with cellulases,corresponding activity units are preferred (e.g. CEVU or cellulaseEquivalent Viscosity Units). For instance, the compositions of thepresent invention can contain cellulase enzymes at a level equivalent toan activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzymepreparations used for the purpose of formulating the compositions ofthis invention typically have an activity comprised between 1,000 and10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.

(K) Liquid Carrier

Another optional, but preferred, ingredient is a liquid carrier. Theliquid carrier employed in the instant compositions is preferably atleast primarily water due to its low cost, relative availability,safety, and environmental compatibility. The level of water in theliquid carrier is preferably at least 50%, most preferably at least 60%,by weight of the carrier. Mixtures of water and low molecular weight,e.g., <200, organic solvent, e.g., lower alcohols such as ethanol,propanol, isopropanol or butanol are useful as the carrier liquid. Lowmolecular weight alcohols include monohydric, dihydric (glycol, etc.)trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.

(L) Other Optional Ingredients

The present invention can include optional components conventionallyused in textile treatment compositions, for example: colorants;preservatives; surfactants; anti-shrinkage agents; fabric crispingagents; spotting agents; germicides; fungicides; anti-oxidants such asbutylated hydroxy toluene, anti-corrosion agents, enzyme stabilisers,materials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process (i.e., dye transfer inhibitingagents), hydrotropes, processing aids, dyes or pigments, and the like.

The present invention can also include other compatible ingredients,including those as disclosed in WO96/02625, WO96121714, and WO96/21715.

Form of the Composition

The composition of the invention may take a variety of physical formincluding liquid, gel, foam in either aqueous or non-aqueous form,granular and tablet forms.

When in a liquid form, the composition may also be dispensed by adispensing means such as a spray dispenser, or aerosol dispenser.

Spray Dispenser

The present invention also relates to such compositions incorporatedinto a spray dispenser to create an article of manufacture that canfacilitate treatment of fabric articles and/or surfaces with saidcompositions containing the amine reaction product and other ingredients(examples are cyclodextrins, polysaccharides, polymers, surfactant,perfume, softener) at a level that is effective, yet is not discerniblewhen dried on the surfaces. The spray dispenser comprises manuallyactivated and non-manual powered (operated) spray means and a containercontaining the treating composition. Typical disclosure of such spraydispenser can be found in WO 96/04940 page 19 line 21 to page 22 line27. The articles of manufacture preferably are in association withinstructions for use to ensure that the consumer applies sufficientingredient of the composition to provide the desired benefit. Typicalcompositions to be dispensed from a sprayer contain a level of aminereaction product of from about 0.01% to about 5%, preferably from about0.05% to about 2%, more preferably from about 0.1% to about 1%, byweight of the usage composition.

Method of Use

Also provided herein is a method for providing a delayed release of anactive ketone or aldehyde which comprises the step of contacting thesurface to be treated with a compound or composition of the invention,and thereafter subjecting the treated surface with a material,preferably an aqueous medium like moisture or any other meanssusceptible of releasing the active from the amine reaction product.

By “surface”, it is meant any surface onto which the compound candeposit. Typical examples of such material are fabrics, hard surfacessuch as dishware, floors, bathrooms, toilet, kitchen, skin, and othersurfaces in need of a delayed release of an active ketone or aldehydesuch as that with litter like animal litter. Preferably, the surface isa fabric.

By “delayed release” is meant release of the active component (e.gperfume) over a longer period of time than by the use of the active(e.g., perfume) itself.

Abbreviations Used in the Following Invention Composition Examples

In the composition examples, the abbreviated component identificationshave the following meanings:

DEQA: Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride DTDMAC:Ditallow dimethylammonium chloride DEQA (2): Di-(soft-tallowyloxyethyl)hydroxyethyl methyl ammonium methylsulfate. DTDMAMS: Ditallow dimethylammonium methylsulfate. SDASA: 1:2 ratio of stearyldimethylamine:triple-pressed stearic acid. Fatty acid: Stearic acid of IV = 0Electrolyte: Calcium chloride PEG: Polyethylene Glycol 4000 NeodolC14-C15 linear primary alcohol ethoxylate, sold by 45-13: Shell ChemicalCO. Cellulase: Cellulytic enzyme sold under the tradename Carezyme,Celluzyme and/or Endolase by Novo Nordisk A/S. SiliconePolydimethylsiloxane foam controller with siloxane- antifoam:oxyalkylene copolymer as dispersing agent with a ratio of said foamcontroller to said dispersing agent of 10:1 to 100:1. PEI:Polyethyleneimine with an average molecular weight of 1800 and anaverage ethoxylation degree of 7 etholeneoxy residues per nitrogen HEDP:1,1-hydroxyethane diphosphonic acid ARP1: Amine reaction product ofethyl 4-aminobenzoate with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde asmade from Synthesis example I ARP2: Amine reaction product ofaminobenzoic acid with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde madeaccording to Synthesis example I ARP3: Amine reaction product of LupasolP with α- Damascone as made from Synthesis example III ARP4: Aminereaction product of D-glucamine with Citronellal as made from Synthesisexample II ARP5: Amine reaction product of LupasolHF with δ-Damascone asmade from Synthesis example III Polymer: Polyvinylpyrroiidone K90available from BASF under the tradename Luviskol K90 Dye fixative: Dyefixative commercially available from Clariant under the tradenameCartafix CB Polyamine: 1,4-Bis-(3-aminopropyl)piperazine Bayhibit2-Phosphonobutane-1,2,4-tricarboxylic acid AM: commercially availablefrom Bayer Fabric Di-(canoloyl-oxy-ethyl)hydroxyethyl methyl softenerammonium methylsulfate active: HPBDC: Hydroxypropyl beta-cyclodextrinRAMEB: Randomly methylated beta-cyclodextrin Bardac 2050: Dioctyldimethyl ammonium chloride, 50% solution Bardac Didecyl dimethylammonium chloride, 50% solution 22250: Genamin Coco fatty amineethoxylated with 10 moles ethylene C100: oxide and commerciallyavailable from Clariant Genapol Coco alcohol ethoxylated with 10 molesethylene V4463: oxide and commercially available from Clariant Silwet7604: Polyalkyleneoxide polysiloxanes of MW 4000 of formula R-(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R)SiO]_(b)—Si(CH₃)₂-R, wherein averagea + b is 21, and commercially available from Osi Specialties, Inc.,Danbury, Connecticut Silwet 7600: Polyalkyleneoxide polysiloxanes of MW4000, of formula R-(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R)SiO]_(b)—Si(CH₃)₂-R, wherein averagea + b is 11, and commercially available from Osi Specialties Inc.,Danbury, Connecticut

The following are synthesis examples of compounds according to theinvention:

I-Synthesis of ethyl 4-aminobenzoate with2.4-dimethyl-3-cyclohexen-1-carboxaldehyde

To an ice cooled stirred solution of 10 g of2,4-dimethyl-3-cyclohexen-1-carboxaldehyde (0.07 mol) in 35 mL EtOH andmolecular sieves (4 Å, 20 g) 1 eq of the amine was added via an additionfunnel. The reaction mixture was stirred under nitrogen atmosphere andprotected from light. After 6 days the mixture was filtrated and thesolvent was removed. The yield of imine formation is about 90%.

Similar results were obtained where the2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by bourgeonal,or trans-2-nonenal. Additionally, similar results were obtained wherethe ethyl-4-aminobenzoate was replaced by 4-amino benzoic acid.

II-Synthesis of D-glucamine with2,4-dimethyl-3-cyclohexen-1-carboxaldehyde

To an ice cooled solution of 1 mmol D-glucamine in about 30 mL EtOH andmolecular sieves (4 Å, 5 g) 1 eq of the2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was added. The reaction wasstirred under nitrogen atmosphere and protected from light. After 3 to 4days, the molecular sieves and the solvent were removed by filtrationand evaporation respectively. The solid imine was obtained in 85 to 90%yield.

Similar results were obtained where the2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by citronellal,trans-2-nonenal, or decanal.

III-Synthesis of Lupasol with Damascone

The β-amino ketone from Lupasol G100 (commercial available by BASFcontent 50% water, 50% Lupasol G100 (Mw. 5000)) and α-Damascone wasprepared using any one of these three different procedures described asfollows:

1. Commercially available Lupasol G100 was dried using the followingprocedure: 20 g of the Lupasol solution was dried at the rotatingevaporator during several hours. The obtained residue, still containingabout 4.5 g of H₂O, was azeotropically distilled at the rotatingevaporator using toluene. The residue was then placed in the desiccatordried at 60° C. (using P₂O₅ as water absorbing material). On basis ofthe obtained weight we concluded that the oil contained less then 10%H₂O. On basis of the NMR-spectra we concluded that this is probably lessthen 5%. This dried sample was then used in the preparation of β-aminoketones.

1.38 g of the dried Lupasol G100 was dissolved in 7 ml. ethanol. Thesolution was stirred gently with a magnetic stirrer during a few minutesbefore 2 g Na₂SO₄ (anhydrous) was added. After stirring again for a fewminutes 2.21 g α-Damascone was added over a period of 1 minute. Aftertwo days reaction, the mixture was filtrated over a Celite filter (videsupra), and the residue washed thoroughly with ethanol. About 180 ml. ofa light foaming filtrate was obtained. This was concentrated untildryness using a rotating evaporator and dried over P₂O₅ in an desiccatorat room temperature. About 3.5 of a colorless oil was obtained.

2. 4.3 g Lupasol G100 solution was (without drying) dissolved in 10 ml.ethanol. The solution was stirred with a magnetic stirrer during a fewminutes before 3.47 g α-Damascone was added over a 1.5 minutes period.After two days reaction at room temperature the reaction mixture wasfiltrated over Celite (vide supra) and the residue washed thoroughlywith ethanol. The filtrate (200 ml., light foaming) was concentrated atthe evaporator and dried in an desiccator (P₂O₅ as drying agent) at roomtemperature. About 6.0 g of a colorless oil was obtained.

3. To about 3.0 g of Lupasol G100 solution (used as such) was added 2.419 α-Damascone. The mixture was stirred without using solvent. Afterstirring for 4 days the obtained oil was dissolved in 100 ml. THF, driedwith MgSO₄, filtrated and the filtrate concentrated at the rotatingevaporator. After drying in the exsiccator (P₂O₅) at room temperature,about 4.1 g of a colorless oil was obtained. This oil still containedabout 13% (w/w) of THF, even after a prolonged drying (3 days).

The product obtained from the three procedures had identicalNMR-spectra.

The β-amino ketone from Lupasol P and α-Damascone was prepared using theprocedure described as follows:

About 1.8 g Lupasol P solution (50% H₂O, 50% Lupasol Mw. 750000, asobtained from BASF) was dissolved in 7 ml ethanol, the solution wasstirred for a few minutes with a magnetic stirrer before 1.44 gα-Damascone was added. After three days the reaction mixture wasfiltrated over a celite filter (vide supra) and the residue washedthoroughly with ethanol. After concentrating of the filtrate and dryingof the obtained oil in the desiccator (P₂O₅) at room temperature, about3 g of the reaction product between Lupasol and α-Damascone wasobtained.

In the following formulation examples all levels are quoted as % byweight of the composition unless otherwise stated, and incorporation ofthe amine reaction product so called herein after “ARP” in the fullyformulated composition is carried out by dry addition (d), encapsulationin starch (es) as described in GB-1,464,616 or cyclodextrin (ec) or asis in the composition as defined herein before. The term in bracket forthe ARP in the formulation examples refers to the means ofincorporation. When none is provided, the incorporation is made as itis. The levels given for the ARP, whether processed or not, refer to thelevel of ARP as is and not to the processed ARP.

EXAMPLE 1

The following fabric softening compositions are in accordance with thepresent invention

Component A B C D E F G H DTDMAC — — — — — 4.5 15.0 15.0 DEQA 2.6 2.918.0 18.0 19.0 — — — Fatty acid 0.3 — 1.0 1.0 — — — — HCl 0.02 0.02 0.020.02 0.02 0.02 0.02 0.02 PEG — — 0.6 0.6 0.6 — 0.6 0.6 Perfume 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 Silicone antifoam 0.01 0.01 0.01 0.01 0.01 0.010.01 0.01 ARP 5 0.3 — 0.2 0.2 — — — 0.2 ARP 3 — 0.05 — — 0.2 — 0.4 0.4ARP 4 — — — 0.02 — 0.05 — — Electrolyte (ppm) — — 600 600 1200 — 12001200 Dye (ppm) 10 10 50 50 50 10 50 50 Water and minors to balance to100%

EXAMPLE 2

The following rinse added fabric softener composition was preparedaccording to the present invention:

A B C D E DEQA (2) 20.0 20.0 20.0 20.0 20.0 ARP1 0.5 — — — — ARP2 — 0.3— 0.04 ARP3 — 0.1 0.1 — — ARP4 — — — 0.1 0.1 Cellulase 0.001 0.001 0.0010.001 0.001 HCL 0.03 0.03 0.03 0.03 0.03 Silicon Antifoam 0.01 0.01 0.010.01 0.01 Blue dye 25 ppm 25 ppm 25 ppm 25 ppm 25 ppm Electrolyte 0.200.20 0.20 0.20 0.20 Perfume 0.90 0.90 0.90 0.90 0.90 Miscellaneous Up to100% and water

EXAMPLE 3

The following fabric softener compositions were prepared according tothe present invention :

A B C D E F G H DEQA 2.6 2.6 2.6 2.6 19.0 19.0 19.0 19.0 Fatty acid 0.30.3 0.3 0.3 — — — — Hydrochloride acid 0.02 0.02 0.02 0.02 0.02 0.020.02 0.02 ARP 1 0.02 — — — — 0.1 0.23 0.2 ARP 5 — 0.2 0.2 — — — — 0.1ARP 3 — — 0.2 0.05 0.3 0.2 — 0.2 Perfume 10 1.0 1.0 1.0 1.0 1.0 1.0 1.0PEI — 0.5 0.3 0.3 — 2.0 1.5 1.5 HEDP — — 0.05 0.05 — — 0.3 0.3 Siliconeantifoam 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Electrolyte — — — — 0.10.1 0.1 0.1 Dye 10 ppm 10 ppm 10 ppm 10 ppm 25 ppm 25 ppm 25 ppm 25 ppmWater and minors 100% 100% 100% 100% 100% 100% 100% 100%

EXAMPLE 4

The following dryer added fabric conditioner compositions were preparedaccording to the present invention:

A B C D E F G DEQA (2) — — — — 51.8 51.8 51.8 DTMAMS — — 26.0 26.0 — — —SDASA 70.0 70.0 42.0 42.0 40.2 40.2 40.2 Neodol 45-13 13.0 13.0 — — — —— Ethanol 1.0 1.0 — — — — — ARP 1 (es) 0.1 — — 0.1 0.2 — — ARP 2 (ec) —0.1 — — — — — ARP 3 (es) — — 0.05 — — 0.2 — ARP 5 (d) — — — — — — 0.3Perfume 0.75 0.75 1.0 1.0 1.5 1.5 1.5 Glycoperse — — — — 15.4 15.4 15.4S-20 Glycerol mono- — — 26.0 26.0 — — — stearate Digeranyl 0.38 0.38 — —— — — Succinate Clay — — 3.0 3.0 — — — Dye 0.01 0.01 — — — — —

EXAMPLE 5

The following are non-limiting examples of pre-soak fabric conditioningand/or fabric enhancement compositions according to the presentinvention which can be suitably used in the laundry rinse cycle:

Ingredients A B C D E F Polymer 3.5 3.5 3.5 3.5 3.5 3.5 Dye fixative 2.32.3 2.4 2.4 2.5 2.5 Polyamine 15.0 15.0 17.5 17.5 20.0 20.0 Bayhibit AM1.0 1.0 1.0 1.0 1.0 1.0 C₁₂-C₁₄ dimethyl hydroxyethyl — 5.0 5.0 — — —quatemary ammonium chloride Fabric softener active — — 2.5 2.5 — —Genamin C100 0.33 — 0.33 0.33 0.33 — Genapol V4463 0.2 — 0.2 0.2 0.2 —ARP1 1.0 2.0 0.1 0.5 0.05 0.08 Water & minors balance balance balancebalance balance balance

EXAMPLE 6

The following are non-limiting examples of odor-absorbing compositionssuitable for spray-on applications:

Examples A B C D E Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % HPBCD 1.0 —1.0 — 1.2 RAMEB — 1.0 — 0.8 — Tetronic 901 — — 0.1 — — Silwet L-7604 — —— 0.1 — Silwet L-7600 0.1 — — — 0.1 Bardac 2050 — — — 0.03 — Bardac 2250— 0.2 — — 0.1 Diethylene glycol — 1.0 — — 0.2 Triethylene glycol — — 0.1— — Ethanol — — — — 2.5 Perfume 1 0.1 — — — — Perfume 2 — 0.05 — 0.1 —Perfume 3 — — 0.1 — 0.1 Kathon 3 ppm 3 ppm 3 ppm 3 ppm — HCl to pH 4.5to pH 4.5 to pH 3.5 to pH 3.5 to pH 3.5 ARP1 5.0 1.0 — — — ARP3 — — 0.50.1 0.08 Distilled water Bal. Bal. Bal. Bal. Bal.

The perfume 1, 2, and 3 have the following compositions:

Perfume 1 2 3 Perfume Ingredients Wt. % Wt. % Wt. % Anisic aldehyde — —2 Benzophenone 3 5 — Benzyl acetate 10 15 5 Benzyl salicylate 5 20 5Cedrol 2 — — Citronellol 10 — 5 Coumarin — — 5 Cymal — — 3Dihydromyrcenol 10 — 5 Flor acetate 5 — 5 Galaxolide 10 — — Lilial 10 1520 Linalyl acetate 4 — 5 Linalool 6 15 5 Methyl dihydro jasmonate 3 10 5Phenyl ethyl acetate 2 5 1 Phenyl ethyl alcohol 15 15 20 alpha-Terpineol5 — 8 Vanillin — — 1 Total 100 100 100

What is claimed is:
 1. A perfume releasing compound, said compound isthe reaction product of: a) an amine having the formula:

 wherein R is C₂-C₁₂ alkylene, R′ is hydrogen, m is from 2 to 700, n isfrom 0 to 350, m+n is at least 5, said amine having an Odor IntensityIndex of less than a 1% solution of methyl anthranilate in dipropyleneglycol; b) an aldehyde perfume, a ketone perfume, and mixtures thereof;wherein said perfume releasing compound has a Dry Surface Odor Index ofmore than
 5. 2. A perfume releasing compound, said compound is thereaction product of: a) an amine having the formula:

 wherein the indices m and n are selected such that saidpolyethyleneimine has a molecular weight of from 150 to 2,000,000, saidamine having an Odor Intensity Index of less than a 1% solution ofmethyl anthranilate in dipropylene glycol; b) an aldehyde perfume, aketone perfume, and mixtures thereof; wherein said perfume releasingcompound has a Dry Surface Odor Index of more than
 5. 3. A compoundaccording to claim 2 wherein said polyethyleneimine has a molecularweight of from 400 to 1,000,000.
 4. A compound according to claim 3wherein said polyethyleneimine has a molecular weight of from 5000 to1,000,000.
 5. A compound according to claim 2 wherein said aldehydeperfume has an Odor Detection Threshold less than or equal to 1 ppm. 6.A compound according to claim 2 wherein said aldehyde perfume comprisesat least 5 carbon atoms.
 7. A compound according to claim 2 wherein saidaldehyde perfume is selected from the group consisting of ligustral,triplal, florhydral, Floralozone, cyclal C, 1-decanal, benzaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,3,7-dimetyl-2,6-octadien-1-al, heliotropin,2,4,6-trimethyl-3-cyclohexen-1-carboxaldehyde, 2,6-nonadienal, α-n-amylcinnamic aldehyde, α-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral,cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, burgeonal,and mixtures thereof.
 8. A compound according to claim 2 wherein saidaldehyde perfume has an Odor Detection Threshold less than or equal to 1ppm.
 9. A compound according to claim 2 wherein said aldehyde perfumecomprises at least 5 carbon atoms.
 10. A compound according to claim 2wherein said ketone perfume is selected from the group consisting ofα-damascone, β-damascone, δ-damascone, isodamascone, carvone, α-ionone,β-ionone, δ-ionone γ-methyl ionone, iso-E-Super,2,4,4,7-tetramethyloct-6-en-3-one, benzyl acetone, damascenone, methyldihydrojasmonate, methyl cedrylone, and mixtures thereof.
 11. A perfumereleasing compound comprising the reaction product of: a) an aminehaving the formula:

 wherein R is C₂-C₁₂ alkylene, R′ is hydrogen, m is from 2 to 700, n isfrom 0 to 350, m+n is at least 5, said amine having an Odor IntensityIndex of less than a 1% solution of methyl anthranilate in dipropyleneglycol; b) an aldehyde perfume, a ketone perfume, and mixtures thereof,wherein said aldehyde and ketone has an Odor Detection Threshold lessthan or equal to 1 ppm; wherein said compound has a Dry Surface OdorIndex of more than
 5. 12. A compound according to claim 11 wherein saidperfume releasing compound comprises from 10% to 90% by weight, of analdehyde or a ketone.
 13. A compound according to claim 11 wherein theindex m has the value from 4 to 400.